CN116444956A - Biodegradable material composition, preparation method thereof and film product - Google Patents
Biodegradable material composition, preparation method thereof and film product Download PDFInfo
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- CN116444956A CN116444956A CN202210012139.2A CN202210012139A CN116444956A CN 116444956 A CN116444956 A CN 116444956A CN 202210012139 A CN202210012139 A CN 202210012139A CN 116444956 A CN116444956 A CN 116444956A
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- 239000000203 mixture Substances 0.000 title claims abstract description 57
- 239000000463 material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 30
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 30
- 239000004970 Chain extender Substances 0.000 claims abstract description 28
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 24
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 24
- 239000000454 talc Substances 0.000 claims abstract description 17
- 229910052623 talc Inorganic materials 0.000 claims abstract description 17
- 235000012222 talc Nutrition 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 13
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 claims abstract 16
- 238000000034 method Methods 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 17
- 238000000071 blow moulding Methods 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 14
- 239000002861 polymer material Substances 0.000 abstract description 2
- -1 polybutylene terephthalate-polybutylene succinate copolymer Polymers 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000011020 pilot scale process Methods 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 239000002826 coolant Substances 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- ZMKVBUOZONDYBW-UHFFFAOYSA-N 1,6-dioxecane-2,5-dione Chemical compound O=C1CCC(=O)OCCCCO1 ZMKVBUOZONDYBW-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000012809 cooling fluid Substances 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000010096 film blowing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/02—Polyalkylene oxides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to the technical field of high polymer materials, and discloses a biodegradable material composition, a preparation method thereof and a film product, wherein the composition comprises the following raw materials: PBST, talc, polyethylene glycol, optionally a chain extender and optionally an antioxidant; based on the total weight of PBST and talcum powder, the dosage of PBST is 85-99 wt%, and the dosage of talcum powder is 1-15 wt%; the dosage of polyethylene glycol is 2-15% of the total weight of PBST and talcum powder, the dosage of chain extender is 0-5% of the total weight of PBST and talcum powder, and the dosage of antioxidant is 0-1.5% of the total weight of PBST and talcum powder. The film product prepared by the composition has stable size, difficult adhesion, uniform thickness, good comprehensive performance and high production speed.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a biodegradable material composition, a preparation method of the biodegradable material composition and a film product prepared from the biodegradable material composition.
Background
With the continuous improvement of environmental protection standards, the use of biodegradable plastics which are more environment-friendly to replace traditional non-degradable plastics is a trend, and particularly in the field of films, such as application fields of express packaging films, supermarket shopping bags and the like, the biodegradable materials have very wide development prospects. The common process types in film processing are a calendaring method, a blow molding method, a casting method, a stretching method and the like, and the blown film process has strong raw material adaptability and is one of the most common processing modes used in all films. In the blown film process, the production line speed is increased, and the optimization of the uniformity of the film thickness has important significance in the production efficiency and the product quality control.
Disclosure of Invention
In order to improve production efficiency and product quality, the invention aims to provide a biodegradable material composition, a preparation method thereof and a film product, wherein the composition is suitable for rapid production, is suitable for various blow molding processes such as flat blowing, up blowing and down blowing, and has the advantages of high speed of a blow molding production line, stable film product size, difficult bonding, uniform thickness and good comprehensive performance.
In a first aspect the present invention provides a biodegradable material composition, the composition consisting of: PBST, talc, polyethylene glycol, optionally a chain extender and optionally an antioxidant;
based on the total weight of PBST and talcum powder, the dosage of PBST is 85-99 wt%, and the dosage of talcum powder is 1-15 wt%; the dosage of polyethylene glycol is 2-15% of the total weight of PBST and talcum powder, the dosage of chain extender is 0-5% of the total weight of PBST and talcum powder, and the dosage of antioxidant is 0-1.5% of the total weight of PBST and talcum powder.
The second aspect of the present invention provides a method for preparing the above biodegradable material composition, the method comprising: adding the raw materials into a high-speed stirrer for mixing to obtain a mixed material; and adding the mixed material into a double-screw extruder for melting, and extruding and granulating to obtain the biodegradable material composition.
In a third aspect the present invention provides a biodegradable film article prepared from the composition described above.
The film product prepared by the composition has good comprehensive mechanical property, simple preparation method, low cost, stable film bubble, uniform film thickness, no folds and no adhesion in the processing process, and can realize rapid and stable production.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
According to a first aspect of the present invention there is provided a biodegradable material composition, the composition consisting of: PBST, talc, polyethylene glycol, optionally a chain extender and optionally an antioxidant;
based on the total weight of PBST and talcum powder, the dosage of PBST is 85-99 wt%, and the dosage of talcum powder is 1-15 wt%; the dosage of polyethylene glycol is 2-15% of the total weight of PBST and talcum powder, the dosage of chain extender is 0-5% of the total weight of PBST and talcum powder, and the dosage of antioxidant is 0-1.5% of the total weight of PBST and talcum powder.
In the present invention, the PBST (polybutylene terephthalate-polybutylene succinate copolymer) is a copolymer containing a repeating unit represented by the formulas (I) and (II);
in the formula (I), m 1 ＝4，n 1 ＝2；
In the PBST, the content of the repeating unit shown in the formula (II) is 45-55 mol%.
According to the invention, the talc has a particle size of 325 to 8000 mesh, preferably 2000 to 8000 mesh.
In the invention, the molecular weight of the polyethylene glycol is 200-600g/mol.
Preferably, PBST is used in an amount of 90 to 99% by weight and talc is used in an amount of 1 to 10% by weight, based on the total weight of PBST and talc.
According to the present invention, the chain extender and the antioxidant may be of various types conventionally used in the art. For example, the antioxidant may be a hindered phenolic antioxidant, a phosphite antioxidant, a pentaerythritol ester antioxidant; the chain extender may be a difunctional acid derivative, isocyanate, anhydride, epoxide.
In the present invention, various raw materials may be prepared or commercially available, and the source thereof is not particularly limited as long as the above-mentioned parameter requirements are satisfied.
The PBST of the invention can be prepared by the following method, which comprises the following steps:
(1) Contacting and prepolymerizing diacid, ester thereof, anhydride thereof or mixture thereof, glycol and a first catalyst in a reaction kettle under vacuum condition to obtain prepolymer; the diacid refers to organic dicarboxylic acids such as terephthalic acid and succinic acid, and the diol refers to primary dibasic alcohols including butanediol;
(2) And (3) contacting a second catalyst with the prepolymer, and performing vacuum polycondensation reaction to obtain the PBST (polybutylene terephthalate-polybutylene succinate copolymer).
The invention has no special limitation on the mixing sequence of the components in the reaction system, and the dosage of the components is also based on the content of the structural units required by the product.
The reaction conditions of the individual steps according to the invention may also be those conventional in the art.
Specifically, in step (1), the reaction conditions of the prepolymerization may include: the reaction temperature is 190-250 ℃; the vacuum degree is 200-600Pa; the reaction time is 1-3 hours, or until the small molecules in the reaction system are nearly pumped down, the temperature of the fraction is kept unchanged.
In the step (2), the reaction conditions of the vacuum polycondensation reaction may include: the reaction temperature is 200-300 ℃; the vacuum degree is less than 300Pa; the reaction time is 3-12 hours.
The catalyst used in the polymerization reaction and the amount thereof are not particularly limited in the present invention, and various conventional catalysts for synthesizing polyesters and the amount of the conventional catalyst may be used. Wherein the catalysts used in step (1) and step (2) may be the same or different. For example, the catalyst used in step (1) may be selected from at least one of the compounds of the metals titanium, antimony and tin; the catalyst used in step (2) may be selected from the group consisting of compounds of rare earth metals Ln selected from at least one of lanthanoid elements, scandium, and yttrium, and mixtures thereof.
According to the invention, the step (1) and the step (2) can be carried out in the same reaction kettle or in different reaction kettles, namely, the prepolymer can be taken out to another reaction kettle to continue the subsequent polymerization reaction.
According to the present invention, nitrogen protection is generally used in the reaction system, but other atmospheres including air may be filled.
According to a second aspect of the present invention, there is provided a method of preparing the above biodegradable material composition, the method comprising: adding the raw materials into a high-speed stirrer for mixing to obtain a mixed material; and adding the mixed material into a double-screw extruder for melting, and extruding and granulating to obtain the biodegradable material composition.
In the present invention, the mixing time may be 1 to 10 minutes.
In a third aspect the present invention provides a biodegradable film article prepared from the composition described above.
According to the invention, the film product is processed by a blow molding method.
The blow molding method adopted by the invention can be conventionally set according to the prior art, and the following main settings and conditions are applicable:
1) The screw length may be 20 to 40 times the screw diameter.
2) Barrel and die temperatures may be in the range of 110-180 ℃.
3) The blow-up ratio may be 2 to 4.
4) The die diameter may be any commercial die size.
5) Film cooling may be performed with a cooling fluid, which may be liquid or gaseous. In the case of cooling with a liquid cooling medium, water is the preferred cooling medium and the extrusion direction may be vertically downward. In the case of cooling with a gaseous cooling medium, air is the preferred cooling medium, but other gases, such as nitrogen, may also be used, and the extrusion direction is preferably vertically upwards.
6) The cooling medium temperature may be 5 to 20 ℃.
7) Extrusion and blowing devices are film blowing devices known in the art.
The substances and parameters not defined in the present invention can be selected according to the prior art, and are conventional in the art.
The invention will be further illustrated with reference to the following examples. But are not limited by these examples.
In the following examples and comparative examples, the data were obtained as follows:
1. mechanical property testing, all mechanical properties were completed by an Instron 5965 universal tester.
2. The crystallization temperature of the material was determined by a TA company Q-100 DSC, the sample was isothermally heated at 200℃for 5 minutes to eliminate the heat history, and then cooled at 10℃per minute. The crystallization temperature was calculated as the peak temperature of the crystallization peak.
Examples 1-13 illustrate compositions of the present invention and methods of making the same.
Example 1
Polybutylene terephthalate-polybutylene succinate copolymer (PBST) and talcum powder are mixed according to the weight ratio of 99:1, and then 0.1 weight percent of chain extender, 5 weight percent of polyethylene glycol and 0.3 weight percent of antioxidant are added into the mixture. The weight percentages of the chain extender, the polyethylene glycol and the antioxidant are calculated according to the sum of the weight of PBST and the weight of talcum powder. Wherein, the polybutylene terephthalate-polybutylene succinate copolymer (PBST) is a pilot-scale product of Beijing chemical industry research institute, and the molar content of the repeating unit (II) is 50 percent. Talc powder is from Michelin Corp, 5000 mesh. The chain extender is BASF corporationADR4468. Polyethylene glycol was obtained from Shanghai Ala Biochemical technologies Co., ltd and had a molecular weight of 600g/mol. The antioxidant is prepared by mixing BASF1010 and BASF168 according to a weight ratio of 1:1. Mixing the raw materials in a high-speed stirrer for 5min, melting the obtained mixture by a double-screw extruder, extruding and granulating to obtain the composition.
The resulting composition was processed into film articles by blow molding, and the specific production conditions and film properties are shown in Table 1.
Example 2
The procedure is as in example 1, except that polybutylene terephthalate-polybutylene succinate copolymer (PBST) and talc are compounded in a weight ratio of 95:5.
Example 3
The procedure is as in example 1, except that the polybutylene terephthalate-polybutylene succinate copolymer (PBST) and talc are formulated in a weight ratio of 90:10.
Example 4
The procedure is as in example 1, except that polybutylene terephthalate-polybutylene succinate copolymer (PBST) and talc are compounded in a weight ratio of 85:15.
Example 5
The difference is that the particle size of talc was changed to 8000 mesh as in example 1.
Example 6
The difference is that the particle size of talc was changed to 2000 mesh as in example 1.
Example 7
The difference was that the particle size of talc was changed to 325 mesh as in example 1.
Example 8
The same as in example 1 was conducted except that the weight fraction of polyethylene glycol was adjusted to 15%.
Example 9
The same as in example 1 was conducted except that the weight fraction of polyethylene glycol was adjusted to 2%.
Example 10
The same as in example 1, except that the polyethylene glycol molecular weight was changed to 200g/mol.
Example 11
The procedure is as in example 1, except that the polyethylene glycol molecular weight is changed to 400g/mol.
Example 12
The difference was that the molar content of the repeating unit (II) in the polybutylene terephthalate-polybutylene succinate copolymer (PBST) was 45% as in example 1.
Example 13
The difference was that the molar content of the repeating unit (II) in the polybutylene terephthalate-polybutylene succinate copolymer (PBST) was 55% as in example 1.
Comparative example 1
Taking polybutylene terephthalateA poly (butylene succinate) copolymer (PBST) material, 0.1 weight percent of chain extender and 0.3 weight percent of antioxidant are added into the material. The weight percentages of the chain extender and the antioxidant are calculated according to the weight of PBST. Wherein, the polybutylene terephthalate-polybutylene succinate copolymer (PBST) is a pilot-scale product of Beijing chemical industry research institute, and the molar content of the repeating unit (II) is 50 percent. The chain extender is BASF corporationADR4468. The antioxidant is prepared by mixing BASF1010 and BASF168 according to a weight ratio of 1:1. Mixing the raw materials in a high-speed stirrer for 5min, melting the obtained mixture by a double-screw extruder, extruding and granulating to obtain the composition.
The resulting composition was processed into film articles by blow molding, and the specific production conditions and film properties are shown in Table 1.
Comparative example 2
A polybutylene terephthalate-polybutylene succinate copolymer (PBST) was taken, and 0.1% by weight of a chain extender, 5% by weight of polyethylene glycol, and 0.3% by weight of an antioxidant were added to the above-mentioned materials. The weight percentages of the chain extender, the polyethylene glycol and the antioxidant are calculated according to the weight of PBST. Wherein, the polybutylene terephthalate-polybutylene succinate copolymer (PBST) is a pilot-scale product of Beijing chemical industry research institute, and the molar content of the repeating unit (II) is 50 percent. The chain extender is BASF corporationADR4468. Polyethylene glycol was obtained from Shanghai Ala Biochemical technologies Co., ltd and had a molecular weight of 600g/mol. The antioxidant is prepared by mixing BASF1010 and BASF168 according to a weight ratio of 1:1. Mixing the raw materials in a high-speed stirrer for 5min, melting the obtained mixture by a double-screw extruder, extruding and granulating to obtain the composition.
The resulting composition was processed into film articles by blow molding, and the specific production conditions and film properties are shown in Table 1.
Comparative example 3
Polybutylene terephthalate-polybutylene succinate copolymer (PBST) and talcum powder are mixed according to the weight ratio of 99:1, and then 0.1 weight percent of chain extender and 0.3 weight percent of antioxidant are added into the mixture. The weight percentages of the chain extender and the antioxidant are calculated according to the sum of the weight of PBST and the weight of talcum powder. Wherein, the polybutylene terephthalate-polybutylene succinate copolymer (PBST) is a pilot-scale product of Beijing chemical industry research institute, and the molar content of the repeating unit (II) is 50 percent. Talc powder is from Michelin Corp, 5000 mesh. The chain extender is BASF corporationADR4468. The antioxidant is prepared by mixing BASF1010 and BASF168 according to a weight ratio of 1:1. Mixing the raw materials in a high-speed stirrer for 5min, melting the obtained mixture by a double-screw extruder, extruding and granulating to obtain the composition.
The resulting composition was processed into film articles by blow molding, and the specific production conditions and film properties are shown in Table 1.
Comparative example 4
The polybutylene terephthalate-polybutylene succinate copolymer (PBST) and talcum powder are mixed according to the weight ratio of 80:20, and then 0.1 weight percent of chain extender, 5 weight percent of polyethylene glycol and 0.3 weight percent of antioxidant are added into the mixture. The weight percentages of the chain extender, the polyethylene glycol and the antioxidant are calculated according to the sum of the weight of PBST and the weight of talcum powder. Wherein, the polybutylene terephthalate-polybutylene succinate copolymer (PBST) is a pilot-scale product of Beijing chemical industry research institute, and the molar content of the repeating unit (II) is 50 percent. Talc powder is from Michelin Corp, 5000 mesh. The chain extender is BASF corporationADR4468. Polyethylene glycol was obtained from Shanghai Ala Biochemical technologies Co., ltd and had a molecular weight of 600g/mol. The antioxidant is prepared by mixing BASF1010 and BASF168 according to a weight ratio of 1:1. The raw materials are firstly treated in the following stepsMixing in a high-speed stirrer for 5min, melting the obtained mixture by a double-screw extruder, extruding and granulating to obtain the composition.
The resulting composition was processed into film articles by blow molding, and the specific production conditions and film properties are shown in Table 1.
Comparative example 5
Polybutylene terephthalate-polybutylene succinate copolymer (PBST) and talcum powder are mixed according to the weight ratio of 99:1, and then 0.1 weight percent of chain extender, 5 weight percent of glycerol and 0.3 weight percent of antioxidant are added into the mixture. The weight percentages of the chain extender, the glycerol and the antioxidant are calculated according to the sum of the weight of PBST and the weight of talcum powder. Wherein, the polybutylene terephthalate-polybutylene succinate copolymer (PBST) is a pilot-scale product of Beijing chemical industry research institute, and the molar content of the repeating unit (II) is 50 percent. Talc powder is from Michelin Corp, 5000 mesh. The chain extender is BASF corporationADR4468. Glycerol is available from Shanghai Ala Biochemical technologies Co. The antioxidant is prepared by mixing BASF1010 and BASF168 according to a weight ratio of 1:1. Mixing the raw materials in a high-speed stirrer for 5min, melting the obtained mixture by a double-screw extruder, extruding and granulating to obtain the composition.
The resulting composition was processed into film articles by blow molding, and the specific production conditions and film properties are shown in Table 1.
TABLE 1
Note that: MD stands for machine direction and TD stands for transverse direction.
As can be seen from Table 1, the addition of talc powder to the composition of the present invention can raise the crystallization temperature of PBST to 20 deg.C or higher, thus significantly increasing the crystallization solidification rate of the melt, increasing the production speed, and simultaneously improving the stability of the film, avoiding the problems of collapse and wrinkling, etc., and avoiding adhesion. In addition, the addition of talcum powder can also improve the mechanical strength of PBST film products and remarkably improve the processing rate. The content and the grain diameter of talcum powder are in a range which can meet the requirements of rapid processing and stable film, and the obtained film has better balance of rigidity and toughness. Beyond this range, the above-mentioned features are not provided. The polyethylene glycol has the function of obviously improving the breaking elongation of the material, so that the film has good toughness and is not easy to break. It can be seen that the material has a good balance of stiffness and toughness within the required compositional range.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described.
Claims (10)
1. A biodegradable material composition, characterized in that it consists of the following raw materials: PBST, talc, polyethylene glycol, optionally a chain extender and optionally an antioxidant;
based on the total weight of PBST and talcum powder, the dosage of PBST is 85-99 wt%, and the dosage of talcum powder is 1-15 wt%; the dosage of polyethylene glycol is 2-15% of the total weight of PBST and talcum powder, the dosage of chain extender is 0-5% of the total weight of PBST and talcum powder, and the dosage of antioxidant is 0-1.5% of the total weight of PBST and talcum powder.
2. The biodegradable material composition according to claim 1, wherein the PBST is a copolymer containing a repeating unit represented by the formulas (I) and (II);
in the formula (I), m 1 ＝4，n 1 ＝2；
In the PBST, the content of the repeating unit shown in the formula (II) is 45-55 mol%.
3. The biodegradable material composition according to claim 1, wherein the talc has a particle size of 325-8000 mesh.
4. A biodegradable material composition according to claim 3, wherein the talc has a particle size of 2000-8000 mesh.
5. The biodegradable material composition according to claim 1, wherein said polyethylene glycol has a molecular weight of 200-600g/mol.
6. The biodegradable material composition according to claim 1, wherein the PBST is used in an amount of 90-99 wt% and the talc is used in an amount of 1-10 wt%, based on the total weight of PBST and talc.
7. A process for the preparation of a biodegradable material composition according to any one of claims 1-6, characterized in that it comprises: adding the raw materials into a high-speed stirrer for mixing to obtain a mixed material; and adding the mixed material into a double-screw extruder for melting, and extruding and granulating to obtain the biodegradable material composition.
8. The method of preparing a biodegradable material composition according to claim 7, wherein the mixing time is 1-10min.
9. A biodegradable film product, characterized in that it is produced by using the composition according to any one of claims 1 to 6.
10. The biodegradable film article of claim 9, wherein the film article is processed by a blow molding process.
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