CN114395139A - Modified lignin suitable for fully-degradable membrane bags and preparation method thereof - Google Patents

Modified lignin suitable for fully-degradable membrane bags and preparation method thereof Download PDF

Info

Publication number
CN114395139A
CN114395139A CN202210037495.XA CN202210037495A CN114395139A CN 114395139 A CN114395139 A CN 114395139A CN 202210037495 A CN202210037495 A CN 202210037495A CN 114395139 A CN114395139 A CN 114395139A
Authority
CN
China
Prior art keywords
lignin
modified lignin
chloride
modified
degradable membrane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202210037495.XA
Other languages
Chinese (zh)
Inventor
施晓旦
徐丽
金霞朝
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Changfa New Materials Co Ltd
Original Assignee
Shanghai Changfa New Materials Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Changfa New Materials Co Ltd filed Critical Shanghai Changfa New Materials Co Ltd
Priority to CN202210037495.XA priority Critical patent/CN114395139A/en
Publication of CN114395139A publication Critical patent/CN114395139A/en
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08HDERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H6/00Macromolecular compounds derived from lignin, e.g. tannins, humic acids
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38Packaging materials of special type or form
    • B65D65/46Applications of disintegrable, dissolvable or edible materials
    • B65D65/466Bio- or photodegradable packaging materials
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2497/00Characterised by the use of lignin-containing materials

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Mechanical Engineering (AREA)
  • Biochemistry (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

The invention relates to the field of lignin modification, in particular to modified lignin suitable for a fully degradable membrane bag and a preparation method thereof, wherein the preparation method comprises the following steps: and (2) putting a proper amount of dried lignin into a kneader, uniformly stirring, heating to a proper temperature, adding an acyl chloride esterifying agent, adding a catalyst, reacting for a certain time, cooling and discharging. And cooling and discharging after the reaction is finished. The modified lignin has good compatibility with the biodegradable master batch, the mechanical property of the synthetic biodegradable film bag is excellent, the high-value utilization of the lignin can be realized, the preparation cost of the composite material is effectively reduced, and the market competitiveness is improved.

Description

Modified lignin suitable for fully-degradable membrane bags and preparation method thereof
Technical Field
The invention relates to the field of lignin modification, in particular to modified lignin suitable for a fully degradable membrane bag and a preparation method thereof.
Background
In recent years, petroleum energy problems and environmental pollution problems are attracting social attention. Traditional PE and PP polyolefin materials are synthesized from non-renewable fossil energy, and the non-renewable resources are gradually decreased with the increase of the demand of plastics; secondly, after the traditional plastics are used, the traditional plastics are generally treated in a landfill or incineration mode, so that white pollution is caused, and the environmental hazard is more and more serious, therefore, the development and the use of renewable and biodegradable materials are very important.
The lignin is a natural aromatic compound with the largest reserve in nature, and has the properties of thermal stability, biodegradability, ultraviolet resistance, oxidation resistance and the like. Lignin is a byproduct of pulping and papermaking and bioethanol industry, is cheap and easily available, but most of lignin is directly combusted to provide energy for factories.
The biodegradable composite material prepared by blending lignin and PBAT not only can reduce the price of the PBAT material, but also can realize high-value utilization of lignin. In industrial production, a plastic additive is usually required to be added to improve the compatibility, but the addition amount of lignin is still small, and the addition amount of the lignin is improved by modifying the lignin, so that the price of the composite material is effectively reduced, and the composite material has a very good application prospect.
Disclosure of Invention
The invention provides modified lignin suitable for a fully degradable membrane bag and a preparation method thereof, and aims to solve the technical problems of the prior art.
In order to solve the above problems, the present invention provides the following technical solutions: the modified lignin suitable for the fully degradable film bag comprises the following components in parts by weight: 100 parts of lignin, 5-40 parts of acyl chloride esterifying agent and 1-5 parts of catalyst.
Preferably, the specific preparation steps are as follows:
step one, lignin modification, namely, putting a proper amount of dried lignin into a kneader, rotating at the speed of 200 and 300 revolutions, and heating to 50-80 ℃. And (3) after the temperature is stable, slowly spraying the catalyst and the acyl chloride esterifying agent on the surface of the reaction material in sequence, uniformly and fully contacting the materials, reacting for 1-3h, cooling after the reaction is finished, and discharging.
And step two, placing the modified lignin in a 50 ℃ oven for 24-48 h, and crushing by using a crushing agent.
Preferably, in the step (1), the lignin source is obtained by an acid precipitation method, the papermaking black liquor is subjected to heat preservation at 40-60 ℃, the pH value of a system is adjusted to 3-4, and the papermaking black liquor is subjected to suction filtration, cleaning, suction filtration again, drying and crushing.
Preferably, the acyl chloride esterifying agent in the step (1) is one or more of stearoyl chloride, lauroyl chloride, hexadecanoyl chloride, oleoyl chloride and octanoyl chloride.
Preferably, the molar ratio of the lignin unit to the acid chloride in the step (1) is 1: 1-5.
Preferably, in the step (1), the catalyst is one or more of ammonia, triethylamine, diethylamine, pyrimidine and sodium hydroxide. The molar ratio of lignin units to catalyst is 1: 0.2-1.
Preferably, the particle size of the modified lignin after pulverization by the pulverizer in the step (2) is 10 μm or less.
Compared with the prior art, the invention has the beneficial effects that: the modified lignin has good compatibility with the biodegradable master batch, the mechanical property of the synthetic biodegradable film bag is excellent, the high-value utilization of the lignin can be realized, the preparation cost of the composite material is effectively reduced, and the market competitiveness is improved.
Detailed Description
Taking a proper amount of dried lignin, putting the lignin into a kneader, rotating at the speed of 200 and 300 turns, and heating to 50-80 ℃. Adding acyl chloride esterifying agent and catalyst, reacting for 1-3h, cooling and discharging after the reaction. Placing the modified lignin in a 50 ℃ oven for 24-48 h, and crushing.
Example 1
200g of dried lignin is put into a kneader, the rotation speed is 240 r, and the temperature is increased to 80 ℃. Adding stearoyl chloride in a molar ratio of the lignin unit to the acyl chloride of 1:1, adding triethylamine catalyst in a molar ratio of the lignin unit to the triethylamine of 1:0.5, reacting for 3 hours, and cooling and discharging after the reaction is finished. Putting the modified lignin in an oven at 50 ℃ for 48h, and grinding the lignin to a particle size of less than 10 mu m.
Example 2
200g of dried lignin is put into a kneader, the rotation speed is 240 r, and the temperature is raised to 70 ℃. Adding stearoyl chloride in a molar ratio of the lignin unit to the acyl chloride of 1:1, adding triethylamine catalyst in a molar ratio of the lignin unit to the triethylamine of 1:0.5, reacting for 3 hours, and cooling and discharging after the reaction is finished. Putting the modified lignin in an oven at 50 ℃ for 48h, and grinding the lignin to a particle size of less than 10 mu m.
Example 3
200g of dried lignin is put into a kneader, the rotation speed is 240 r, and the temperature is increased to 80 ℃. Adding oleoyl chloride in a molar ratio of the lignin unit to the acyl chloride of 1:3, adding a pyrimidine catalyst in a molar ratio of the lignin unit to the pyrimidine of 1:0.5, reacting for 2 hours, and cooling and discharging after the reaction is finished. Putting the modified lignin in an oven at 50 ℃ for 48h, and grinding the lignin to a particle size of less than 10 mu m.
Example 4
200g of dried lignin is put into a kneader, the rotation speed is 240 r, and the temperature is increased to 80 ℃. Adding oleoyl chloride in a molar ratio of the lignin unit to the acyl chloride of 1:2, adding triethylamine catalyst in a molar ratio of the lignin unit to the triethylamine of 1:1, reacting for 1h, and cooling and discharging after the reaction is finished. Putting the modified lignin in an oven at 50 ℃ for 48h, and grinding the lignin to a particle size of less than 10 mu m.
Application effect implementation
1. Putting the modified lignin, degradable substance degradable resin PBAT (polybutylene terephthalate/adipate), calcium carbonate, glycerol, DCP (dicumyl peroxide) and stearic acid into a high-speed blender together, and mixing for 50min at the rotating speed of 200rpm to obtain a primary mixture. The composition and the content are as follows according to the mass portion:
Figure BDA0003468605540000031
2. and (3) putting the primary mixture into a double-screw extruder for extrusion granulation, wherein the temperature from the first zone to the sixth zone is 175 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃, 190 ℃ of the head temperature, and 190rpm of the screw, and performing melt extrusion to obtain the master batch.
3. And (3) putting the master batch into a film blowing machine, and carrying out blow molding bag making and molding at 195 ℃ to prepare the fully degradable film bag.
Comparative example 1
The fully degradable bag film comprises the following components in parts by weight:
Figure BDA0003468605540000032
Figure BDA0003468605540000041
the above formula is reacted according to the following steps:
1. putting the degradable resin PBAT (poly terephthalic acid/butylene adipate), calcium carbonate, glycerol, DCP (dicumyl peroxide) and stearic acid into a high-speed blender together, and mixing for 50min at the rotating speed of 200rpm to obtain a primary mixture.
2. And (3) putting the primary mixture into a double-screw extruder for extrusion granulation, wherein the temperature from the first zone to the sixth zone is 175 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃, 190 ℃ of the head temperature, and 190rpm of the screw, and performing melt extrusion to obtain the master batch.
3. And (3) putting the master batch into a film blowing machine, and carrying out blow molding bag making and molding at 195 ℃ to prepare the fully degradable film bag.
Comparative example 2
The total degradation and the preparation method thereof comprise the following components in parts by weight:
Figure BDA0003468605540000042
the above formula is reacted according to the following steps:
1. putting the degradable substance degradable resin PBAT (polybutylene terephthalate/adipate), unmodified lignin powder, calcium carbonate, glycerol, DCP (dicumyl peroxide) and stearic acid into a high-speed blender together, and mixing for 40min at the rotating speed of 400rpm to obtain a primary mixture.
2. And (3) putting the primary mixture into a double-screw extruder for extrusion granulation, wherein the temperature from the first zone to the sixth zone is 160 ℃, 170 ℃, 175 ℃, 180 ℃, 155 ℃, 1185 ℃ at the head temperature, and the screw rotation speed is 200rpm, and performing melt extrusion to obtain the master batch.
3. And (3) putting the master batch into a film blowing machine, and carrying out blow molding bag making and molding at 185 ℃ to prepare the fully degradable film bag.
The performance of examples 1-4 and comparative examples was tested by a universal electronic tensile tester (model KY 8000C) according to the standard (GB/T1040.2-2006), and the specific data are shown in Table 1.
Tensile strength/MPa Elongation at break/%
Example 1 18.2 350.3
Example 2 18.9 355.0
Example 3 17.8 345.2
Example 4 17.5 352.8
Comparative example 1 18.5 349.1
Comparative example 2 16.0 331.9
TABLE 1
The results of the data in table 1 show that the lignin modified by extracting the papermaking waste liquid is suitable for the data display of the tensile property and the impact property of the fully-degradable film bag, and the lignin modified by extracting the papermaking waste liquid can meet the use requirements.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (7)

1. The modified lignin suitable for the fully degradable film bag is characterized by comprising the following components in parts by weight: 100 parts of lignin, 5-40 parts of acyl chloride esterifying agent and 1-5 parts of catalyst.
2. The preparation method of the modified lignin suitable for the fully degradable membrane bags according to claim 1, which comprises the following specific preparation steps:
step one, lignin modification, namely, putting a proper amount of dried lignin into a kneader, rotating at the speed of 200 and 300 revolutions, and heating to 50-80 ℃. And (3) after the temperature is stable, slowly spraying the catalyst and the acyl chloride esterifying agent on the surface of the reaction material in sequence, uniformly and fully contacting the materials, reacting for 1-3h, cooling after the reaction is finished, and discharging.
And step two, placing the modified lignin in a 50 ℃ oven for 24-48 h, and crushing by using a crushing agent.
3. The method for preparing the modified lignin suitable for the fully degradable membrane bags according to claim 1, wherein the modified lignin comprises the following components in percentage by weight: in the step (1), the lignin source is obtained by an acid precipitation method, the papermaking black liquor is subjected to heat preservation at 40-60 ℃, the pH value of a system is adjusted to 3-4, and the papermaking black liquor is subjected to suction filtration, cleaning, suction filtration again, drying and crushing.
4. The method for preparing the modified lignin suitable for the fully degradable membrane bags according to claim 1, wherein the modified lignin comprises the following components in percentage by weight: the acyl chloride esterifying agent in the step (1) is one or more of stearoyl chloride, lauroyl chloride, hexadecanoyl chloride, oleoyl chloride and octanoyl chloride.
5. The method for preparing the modified lignin suitable for the fully degradable membrane bags according to claim 1, wherein the modified lignin comprises the following components in percentage by weight: the molar ratio of the lignin unit to the acyl chloride in the step (1) is 1: 1-5.
6. The method for preparing the modified lignin suitable for the fully degradable membrane bags according to claim 1, wherein the modified lignin comprises the following components in percentage by weight: in the step (1), the catalyst is one or more of ammonia water, triethylamine, diethylamine, pyrimidine and sodium hydroxide. The molar ratio of lignin units to catalyst is 1: 0.2-1.
7. The method for preparing the modified lignin suitable for the fully degradable membrane bags according to claim 1, wherein the modified lignin comprises the following components in percentage by weight: the particle size of the modified lignin which is crushed by the crusher in the step (2) is below 10 mu m.
CN202210037495.XA 2022-01-13 2022-01-13 Modified lignin suitable for fully-degradable membrane bags and preparation method thereof Pending CN114395139A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210037495.XA CN114395139A (en) 2022-01-13 2022-01-13 Modified lignin suitable for fully-degradable membrane bags and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210037495.XA CN114395139A (en) 2022-01-13 2022-01-13 Modified lignin suitable for fully-degradable membrane bags and preparation method thereof

Publications (1)

Publication Number Publication Date
CN114395139A true CN114395139A (en) 2022-04-26

Family

ID=81231316

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210037495.XA Pending CN114395139A (en) 2022-01-13 2022-01-13 Modified lignin suitable for fully-degradable membrane bags and preparation method thereof

Country Status (1)

Country Link
CN (1) CN114395139A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114933785A (en) * 2022-04-29 2022-08-23 上海昶法新材料有限公司 Modified lignin/PBAT biodegradable plastic and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102093573A (en) * 2009-12-14 2011-06-15 武侯区巅峰机电科技研发中心 Method for preparing modified lignosulfonate
CN105111461A (en) * 2015-09-23 2015-12-02 广西大学 Method for preparing lignin ester by mechanical activation- solid reaction
CN110615897A (en) * 2019-09-29 2019-12-27 北京林业大学 Microwave-assisted lignin modification method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102093573A (en) * 2009-12-14 2011-06-15 武侯区巅峰机电科技研发中心 Method for preparing modified lignosulfonate
CN105111461A (en) * 2015-09-23 2015-12-02 广西大学 Method for preparing lignin ester by mechanical activation- solid reaction
CN110615897A (en) * 2019-09-29 2019-12-27 北京林业大学 Microwave-assisted lignin modification method

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
陈小娟等: "木质素酰胺制备的工艺研究", 《中国造纸学报》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114933785A (en) * 2022-04-29 2022-08-23 上海昶法新材料有限公司 Modified lignin/PBAT biodegradable plastic and preparation method thereof

Similar Documents

Publication Publication Date Title
CN103159984B (en) All-degradable thermoplastic starch/polylactic acid blend material and preparation method thereof
CN102093681B (en) Toughness-increasing polylactic acid composite material and preparation method thereof
CN112280263B (en) Lignin-based biodegradable polymer composite film and preparation method thereof
CN111471285B (en) Epoxidized lignin modified biodegradable film and preparation method thereof
CN114507426B (en) Modified nano calcium carbonate composite material and preparation method thereof
CN102604164A (en) Master batch capable of fully and biologically degrading plastic film and preparation method thereof
CN109825045A (en) Graphene composite biomass reinforced PBS/PBAT biodegradable composite material and preparation method thereof
Zhu et al. Modification of lignin with silane coupling agent to improve the interface of poly (L-lactic) acid/lignin composites
CN105440602B (en) Coir fibre/poly butylene succinate composite and preparation method thereof
CN108003645A (en) A kind of complete biodegradable stalk injection-moulded plastic and preparation method thereof
CN103881340A (en) Preparation method and application for biomass fibre-aliphatic polyester composite material macromolecular coupling agent
CN109666269A (en) One kind is containing the modified polyadipate/butylene terephthalate composite material and preparation method of nano micro crystal cellulose
CN113801339A (en) Modified lignin and preparation method thereof
CN113248875A (en) Fully-degradable shopping bag film and preparation method thereof
CN114933785A (en) Modified lignin/PBAT biodegradable plastic and preparation method thereof
CN114395139A (en) Modified lignin suitable for fully-degradable membrane bags and preparation method thereof
CN113234304A (en) Biodegradable film material and preparation method of film
CN104194287A (en) Modified poly-adipic acid/butylene terephthalate composite material containing coconut shell flour and preparation method thereof
CN104194288B (en) One gathers hexanodioic acid/butylene terephthalate matrix material and preparation method thereof containing the modification of wild rice stem hull fibres
CN102643523A (en) Modified polylactic acid/polycaprolactone composite material and preparation method thereof
CN112358658A (en) Biodegradable master batch based on peanut shell fibers and preparation method and application thereof
JP4562852B2 (en) Biodegradable and antistatic aliphatic polyester resin composition
CN109401245A (en) A kind of degradable environment-friendly material
CN114349881A (en) Preparation method of modified hemicellulose suitable for PBAT (poly (butylene adipate-co-terephthalate)) degradable membrane bag
CN101831158B (en) Composite crosslinking amylomaize based fully degradable material and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20220426

RJ01 Rejection of invention patent application after publication