CN117449118A - Tear-resistant degradable plastic paper substitute and preparation method thereof - Google Patents
Tear-resistant degradable plastic paper substitute and preparation method thereof Download PDFInfo
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- CN117449118A CN117449118A CN202311564270.0A CN202311564270A CN117449118A CN 117449118 A CN117449118 A CN 117449118A CN 202311564270 A CN202311564270 A CN 202311564270A CN 117449118 A CN117449118 A CN 117449118A
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- 229920006238 degradable plastic Polymers 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims description 18
- 239000000123 paper Substances 0.000 claims abstract description 74
- 239000002131 composite material Substances 0.000 claims abstract description 51
- 229920001131 Pulp (paper) Polymers 0.000 claims abstract description 28
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 21
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 20
- 238000004537 pulping Methods 0.000 claims abstract description 16
- 239000011122 softwood Substances 0.000 claims abstract description 16
- 239000011121 hardwood Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000010009 beating Methods 0.000 claims abstract description 6
- 239000000835 fiber Substances 0.000 claims description 54
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 38
- 239000004626 polylactic acid Substances 0.000 claims description 38
- 229920001046 Nanocellulose Polymers 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 25
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 20
- 229910000077 silane Inorganic materials 0.000 claims description 20
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000003605 opacifier Substances 0.000 claims description 12
- 239000001509 sodium citrate Substances 0.000 claims description 10
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000000839 emulsion Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000009832 plasma treatment Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- NJVOHKFLBKQLIZ-UHFFFAOYSA-N (2-ethenylphenyl) prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1C=C NJVOHKFLBKQLIZ-UHFFFAOYSA-N 0.000 claims description 4
- PSJBSUHYCGQTHZ-UHFFFAOYSA-N 3-Methoxy-1,2-propanediol Chemical compound COCC(O)CO PSJBSUHYCGQTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 3
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims 1
- 239000002689 soil Substances 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 30
- 229920003023 plastic Polymers 0.000 description 24
- 239000004033 plastic Substances 0.000 description 24
- 229920002678 cellulose Polymers 0.000 description 6
- 239000001913 cellulose Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 4
- 229920002522 Wood fibre Polymers 0.000 description 4
- 239000002985 plastic film Substances 0.000 description 4
- 229920006255 plastic film Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000002025 wood fiber Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 241000863480 Vinca Species 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002362 mulch Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21D—TREATMENT OF THE MATERIALS BEFORE PASSING TO THE PAPER-MAKING MACHINE
- D21D1/00—Methods of beating or refining; Beaters of the Hollander type
- D21D1/20—Methods of refining
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/18—Reinforcing agents
- D21H21/20—Wet strength agents
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/38—Corrosion-inhibiting agents or anti-oxidants
Landscapes
- Paper (AREA)
Abstract
The application discloses tear-resistant degradable plastic paper, which is prepared from the following raw materials in parts by weight: 80-100 parts of composite wood pulp, 5-10 parts of wet strength agent, 20-30 parts of opacifying agent, 15-30 parts of composite reinforcing agent and 2-4 parts of antioxidant; the composite wood pulp is prepared by fluffing and pulping a softwood pulp plate and a hardwood pulp plate, and the weight ratio is (6-8): (2-4), wherein the beating degree of the composite wood pulp is 25-45 DEG SR. The application has excellent degradability by adopting the composite wood pulp with a specific proportion and simultaneously matching with the composite reinforcing agent and the antioxidant, can not pollute soil and water for a long time, and has excellent tear resistance and long service life.
Description
Technical Field
The application relates to tear-resistant degradable plastic paper and a preparation method thereof, belonging to the technical field of papermaking.
Background
With the importance of 'white pollution' at home and abroad and the limitation of disposable plastic products, paper, bamboo, wood, grass and other plant fibers are widely developed and utilized, the paper is a packaging material which is currently known to be more environment-friendly, the application scene is very wide, and the paper is used for replacing plastic and is one of the schemes which must be carried out at present. Paper is environmentally friendly than plastic because it can be degraded and also recycled. However, paper has many disadvantages such as no tear resistance, no heat sealing, no good tensile strength, no plastic, no transparency, etc.
The plastic paper substitute is a paper product made from plant fibers such as wood fibers and paper pulp, and can be used for packaging, plastic film mulching and the like. Compared with the common plastic film, the plastic paper has the advantages of biodegradation, environmental protection and the like. The plastic film mulching technology is widely applied to agricultural field crop cultivation, and can improve soil temperature, reduce water loss, inhibit weed growth, prevent plant diseases and insect pests and the like by mulching the ground surface. At present, various common synthetic plastic films are mainly used for the mulching film. However, the common plastic mulching film is difficult to degrade after being used, and can pollute the soil environment.
Therefore, the degradable mulching film technology becomes a current research hot spot, and various degradable materials are used for mulching film research and development, but each has certain disadvantages. The cellulose-based mulch film is used as a wood fiber material, the raw material is renewable and completely biodegradable, but the problems of poor tear resistance, short service life and the like still affect the application and popularization at present.
The Chinese patent CN 116065417A-plastic paper production process discloses that long fibers are mixed by adopting raw material slurry, so that the sizing is facilitated, the structural strength is ensured, cracking is avoided, meanwhile, multiple additives are added for composite molding, the uniformity during sizing is ensured, the oil resistance and acid resistance are improved, the safety and stability of package use are ensured, and the tearing resistance and the service life performance are limited. Chinese patent CN 115926405A-an ultrathin high-strength biodegradable film discloses that the mechanical property is improved by adding nano-modifiers such as cellulose nano-crystals, but if the compatibility with wood pulp is poor, the film is finally used for the mulching film, and the service life and performance index of the film are difficult to reach the required.
Disclosure of Invention
In order to solve the problems, the anti-tearing degradable plastic substitute paper and the preparation method thereof are provided, and the special proportion of composite wood pulp is adopted, and meanwhile, the composite reinforcing agent and the antioxidant are matched, so that the paper has excellent degradability, can not cause long-term pollution to soil and water, and has excellent anti-tearing performance and long service life.
According to one aspect of the application, the tear-resistant degradable plastic substituting paper is provided, and is prepared from the following raw materials in parts by weight: 80-100 parts of composite wood pulp, 5-10 parts of wet strength agent, 20-30 parts of opacifying agent, 15-30 parts of composite reinforcing agent and 2-4 parts of antioxidant; the composite wood pulp is prepared by fluffing and pulping a softwood pulp plate and a hardwood pulp plate, and the weight ratio is (6-8): (2-4), wherein the beating degree of the composite wood pulp is 25-45 DEG SR.
Specifically, the wood pulp combination of the raw materials and the proportion is adopted, the wood fiber of the softwood pulp is slender and tough, a high-strength framework can be provided, the fiber lumen in the hardwood pulp is large, the components of non-crystallization areas such as lignin and the like are more, the binding force between the two matched fibers is high, and the mechanical property and the durability of paper are good.
Optionally, the composite reinforcing agent comprises modified polylactic acid fibers and silane modified nanocellulose, and the weight ratio is 1: (2-4).
Optionally, the modified polylactic acid fiber is prepared by reacting polylactic acid fiber with a grafting compatilizer and a catalyst after plasma treatment, wherein the weight ratio of the polylactic acid fiber to the grafting compatilizer to the catalyst is (8-10): (0.5-1): (0.05-0.2).
Specifically, the preparation method of the modified polylactic acid fiber comprises the steps of using argon gas as working gas for the polylactic acid fiber, wherein the treatment time is 10min, and the power is 800W; then reacts with grafting compatilizer and catalyst for 2h at the temperature of 80 ℃.
Optionally, the grafting compatilizer is ethylene oxide or glycerol monomethyl ether, and the catalyst is one of sodium hydroxide, triethylamine and dimethylaniline.
Specifically, the polylactic acid fiber is subjected to plasma treatment, and the plasma treatment damages molecular chains on the surface of the polylactic acid fiber to form free radicals, so that the surface roughness and the energy are increased, and the interaction between the subsequent grafting compatilizer and the fiber surface is improved; the grafting compatilizer is subjected to chemical reaction with the activated free radicals on the surface of the polylactic acid fiber to form stable covalent bonds, and active functional groups (such as epoxy groups and hydroxyl groups) contained in ethylene oxide and glycerol monomethyl ether are reacted with the free radicals on the surface of the fiber, so that the surface of the fiber is functionalized, the fiber is tightly combined with the composite wood pulp fiber, the tear resistance and strength of the whole paper are improved, and the compatibility is good.
Optionally, the preparation method of the silane modified nanocellulose comprises the steps of adding a silane coupling agent into nanocellulose suspension, uniformly stirring and reacting for 2-4h, centrifuging and drying.
Specifically, the mass concentration of the nano cellulose suspension is 2wt%, the addition amount of the silane coupling agent is 3% of the mass of the nano cellulose suspension, and the drying temperature is 60 ℃.
Specifically, the alkoxy group of the silane coupling agent reacts with the hydroxyl group on the surface of the nano-cellulose to form a stable silica bond (-Si-O-C-), so that the surface of the nano-cellulose has better chemical activity, and simultaneously, the compatibility of the nano-cellulose with other components such as composite wood pulp and the like is improved, particularly at the interface between fibers, thereby being beneficial to improving the structural stability and durability of the plastic paper.
Optionally, the antioxidant is sodium citrate and benzamide, and the weight ratio is 1: (0.3-0.8).
Optionally, the opacifier is an acrylic emulsion or a styrene-acrylate emulsion.
Optionally, the wet strength agent is one of urea formaldehyde resin, melamine formaldehyde resin or polyamide-polypropylene oxide chloride resin.
According to another aspect of the application, the preparation method of the tear-resistant degradable plastic substituted paper is also disclosed, and comprises the following steps:
(1) Fluffing the softwood pulp plate and the hardwood pulp plate, and pulping by a pulping machine;
(2) And adding the composite reinforcing agent, stirring uniformly, adding the opacifier, the wet strength agent and the antioxidant, stirring uniformly, and then entering a paper machine to manufacture the tear-resistant degradable plastic substitute paper.
Optionally, the mass concentration of the fluffing slurry in the step (1) is 4-6%, and the fluffing time is 30-40min; in the step (2), the stirring speed is 200-300rpm, and the mixture is stirred for 15-30min after adding the composite reinforcing agent, and the stirring speed is 80-150g/m 2 Is quantitatively manufactured by paper making。
Benefits of the present application include, but are not limited to:
1. according to the tear-resistant degradable plastic paper, the composite wood pulp is adopted to match the composite reinforcing agent and the antioxidant, and the wood fiber and the high polymer fiber can be finally biodegraded, so that the environment cannot be polluted, and meanwhile, the tear-resistant degradable plastic paper has good tear resistance, is long in service life and can meet the use requirement.
2. According to the tear-resistant degradable plastic paper, the modified polylactic acid fibers and the silane modified nanocellulose are combined, the modified polylactic acid fibers provide structural support, the overall skeleton of the paper is enhanced, the silane modified nanocellulose is combined among the microcosmic-level reinforcing fibers, additional strength and toughness are provided, and the silane modified nanocellulose cooperate to form a supporting network, so that the paper is tougher and tear-resistant when being subjected to physical pressure, and the mechanical strength and the tear-resistant capability of the plastic paper are improved.
3. According to the tear-resistant degradable plastic paper, broad-spectrum antioxidation protection is provided by adopting the combination of sodium citrate and benzamide, the sodium citrate mainly plays a role in removing free radicals and chelating metal ions, and the benzamide prevents oxidation by improving the thermal stability and the light resistance, so that the service life of the plastic paper is prolonged.
4. The preparation method of the tear-resistant degradable plastic paper is simple and feasible in process, low in raw material and equipment requirements, suitable for large-scale popularization and application, and has the condition of large-scale low-cost production.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this application, illustrate embodiments of the application and together with the description serve to explain the application and do not constitute an undue limitation to the application. In the drawings:
fig. 1 is a high resolution Scanning Electron Microscope (SEM) image of the paper substitute of example 1 of the present application.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. The reagents or materials used in the present invention may be purchased in conventional manners, and unless otherwise indicated, they may be used in conventional manners in the art or according to the product specifications. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention.
The preferred methods and materials described in this patent are illustrative only. The polylactic acid fiber, the nano cellulose suspension, the wet strength agent and the opacifier are all commercially available conventional products, the opacifier is OP-301, the pH of the nano cellulose suspension is 6, and the molecular weight of the polylactic acid fiber is 120000-150000. The conventional technology in the prior art is adopted for papermaking and papermaking in the application, the drying temperature is 70 ℃, the coater is from vinca paper testing machine factory, and the beater and the refiner are from KUMAGAI company in Japan. The same method was used for the preparation of the modified polylactic acid fiber in each example.
EXAMPLE 1 substituted Plastic paper 1#
The tear-resistant degradable plastic paper is prepared from the following raw materials in parts by weight: 90 parts of composite wood pulp, 8 parts of wet strength agent, 25 parts of opacifying agent, 20 parts of composite reinforcing agent and 3 parts of antioxidant; the composite wood pulp is prepared by fluffing and pulping a softwood pulp plate and a hardwood pulp plate, and the weight ratio is 6:3, the beating degree of the composite wood pulp is 35 DEG SR.
The composite reinforcing agent comprises modified polylactic acid fibers and silane modified nanocellulose, and the weight ratio is 1:3. the modified polylactic acid fiber is prepared by the reaction of the polylactic acid fiber after plasma treatment with a grafting compatilizer and a catalyst, wherein the weight ratio of the polylactic acid fiber to the grafting compatilizer to the catalyst is 9:1:0.1. the grafting compatilizer is ethylene oxide, and the catalyst is sodium hydroxide. The preparation method of the silane modified nanocellulose comprises the steps of adding a silane coupling agent into nanocellulose suspension, uniformly stirring for reacting for 3 hours, centrifuging and drying to obtain the silane modified nanocellulose. The antioxidant is sodium citrate and benzamide, and the weight ratio is 1:0.5. the opacifier is acrylic resin emulsion. The wet strength agent is urea-formaldehyde resin.
The preparation method comprises the following steps:
(1) Fluffing the softwood pulp plate and the hardwood pulp plate, and pulping by a pulping machine;
(2) Adding the composite reinforcing agent, stirring uniformly, adding the opacifier, the wet strength agent and the antioxidant, stirring uniformly, and then entering a paper machine to manufacture the tear-resistant degradable plastic paper.
Wherein the mass concentration of the fluffing slurry in the step (1) is 5%, and the fluffing time is 35min; the stirring speed in the step (2) is 250rpm, and the mixture is stirred for 20min after adding the composite reinforcing agent, and the stirring speed is 100g/m 2 Is quantitatively manufactured.
Fig. 1 is a microstructure chart of example 1, in which a dense network of fibers, including modified polylactic acid fibers and silane modified nanocellulose, is seen, the fibers are closely packed, exhibit a complex entangled structure, have a high surface area, demonstrate strong bonding forces and good compatibility between fibers, and enhance tear resistance.
EXAMPLE 2 substituted Plastic paper 2#
The tear-resistant degradable plastic paper is prepared from the following raw materials in parts by weight: 80 parts of composite wood pulp, 5 parts of wet strength agent, 20 parts of opacifying agent, 15 parts of composite reinforcing agent and 2 parts of antioxidant; the composite wood pulp is prepared by fluffing and pulping a softwood pulp plate and a hardwood pulp plate, and the weight ratio is 6:2, the beating degree of the composite wood pulp is 30 DEG SR.
The composite reinforcing agent comprises modified polylactic acid fibers and silane modified nanocellulose, and the weight ratio is 1:2. the modified polylactic acid fiber is prepared by the reaction of the polylactic acid fiber after plasma treatment with a grafting compatilizer and a catalyst, wherein the weight ratio of the polylactic acid fiber to the grafting compatilizer to the catalyst is 9:0.5:0.05. the grafting compatilizer is glycerol monomethyl ether, and the catalyst is triethylamine. The preparation method of the silane modified nanocellulose comprises the steps of adding a silane coupling agent into nanocellulose suspension, uniformly stirring for reacting for 2 hours, centrifuging and drying to obtain the silane modified nanocellulose. The antioxidant is sodium citrate and benzamide, and the weight ratio is 1:0.3. the opacifier is styrene-acrylate emulsion. The wet strength agent is melamine formaldehyde resin.
The preparation method comprises the following steps:
(1) Fluffing the softwood pulp plate and the hardwood pulp plate, and pulping by a pulping machine;
(2) Adding the composite reinforcing agent, stirring uniformly, adding the opacifier, the wet strength agent and the antioxidant, stirring uniformly, and then entering a paper machine to manufacture the tear-resistant degradable plastic paper.
Wherein the mass concentration of the fluffing slurry in the step (1) is 4%, and the fluffing time is 30min; the stirring speed in the step (2) is 200rpm, and the mixture is stirred for 15min after adding the composite reinforcing agent, and the stirring speed is 140g/m 2 Is quantitatively manufactured.
EXAMPLE 3 substituted Plastic paper 3#
The tear-resistant degradable plastic paper is prepared from the following raw materials in parts by weight: 100 parts of composite wood pulp, 10 parts of wet strength agent, 30 parts of opacifying agent, 30 parts of composite reinforcing agent and 4 parts of antioxidant; the composite wood pulp is prepared by fluffing and pulping a softwood pulp plate and a hardwood pulp plate, and the weight ratio is 8:4, the beating degree of the composite wood pulp is 40 DEG SR.
The composite reinforcing agent comprises modified polylactic acid fibers and silane modified nanocellulose, and the weight ratio is 1:4. the modified polylactic acid fiber is prepared by the reaction of the polylactic acid fiber after plasma treatment with a grafting compatilizer and a catalyst, wherein the weight ratio of the polylactic acid fiber to the grafting compatilizer to the catalyst is 10:0.5:0.2. the grafting compatilizer is ethylene oxide, and the catalyst is sodium hydroxide. The preparation method of the silane modified nanocellulose comprises the steps of adding a silane coupling agent into nanocellulose suspension, uniformly stirring for reacting for 4 hours, centrifuging and drying to obtain the silane modified nanocellulose. The antioxidant is sodium citrate and benzamide, and the weight ratio is 1:0.8. the opacifier is styrene-acrylate emulsion. The wet strength agent is polyamide polypropylene oxide resin.
The preparation method comprises the following steps:
(1) Fluffing the softwood pulp plate and the hardwood pulp plate, and pulping by a pulping machine;
(2) Adding the composite reinforcing agent, stirring uniformly, adding the opacifier, the wet strength agent and the antioxidant, stirring uniformly, and then entering a paper machine to manufacture the tear-resistant degradable plastic paper.
Wherein the mass concentration of the fluffing slurry in the step (1) is 6%, and the fluffing time is 40min; the stirring speed in the step (2) is 300rpm, and the mixture is stirred for 28min after adding the composite reinforcing agent, and the stirring speed is 90g/m 2 Is quantitatively manufactured.
Comparative example 1 comparative paper substitute 1#
The main difference between comparative example 1 and example 1 is that: in comparative example 1, single softwood pulp was used.
Comparative example 2 comparative paper substitute 2#
The main difference between comparative example 2 and example 1 is that: the ratio of softwood pulp to hardwood pulp in comparative example 2 was 10:1.
Comparative example 3 comparative paper substitute 3#
The main difference between comparative example 3 and example 1 is that: the composite reinforcing agent of comparative example 3 was an unmodified polylactic acid fiber.
Comparative example 4 comparative paper substitute 4#
The main difference between comparative example 4 and example 1 is that: the composite reinforcement used in comparative example 4 was an unsilane modified nanocellulose.
Comparative example 5 comparative paper substitute 5#
The main difference between comparative example 5 and example 1 is that: the composite reinforcing agent in comparative example 5 comprises modified polylactic acid fibers and silane modified nanocellulose in a weight ratio of 2:1.
comparative example 6 comparative paper substitute 6#
The main difference between comparative example 6 and example 1 is that: the antioxidant used in comparative example 6 was sodium citrate alone, and was not used in combination with benzamide.
Experimental example
1. Tear resistance test: the substituted plastic paper 1# -3# and the comparative substituted plastic paper 1# -6# are tested according to the first part of GB/T455-2002 determination of longitudinal tear of paper and paperboard.
2. Degradation test: the plastic substitute paper 1# -3# and the comparison plastic substitute paper 1# -6# are simultaneously buried in the soil (local natural soil) with the same microbial environment, so that the soil is degraded in the natural environment, and the mulching film is taken out every three months to analyze corrosion resistance and degradation. The experimental data are shown in table 1.
TABLE 1 tear resistance and degradable test results
From the data, the plastic substitute paper prepared by the raw materials and the preparation method defined by the application has good tear resistance, is less degraded in the first three months, can basically meet the use requirement of being used as a mulching film for 6 months, exceeds the service life of a common fiber mulching film for 3-4 months, and can basically realize complete degradation in the later period.
The comparative plastic paper # 1 adopts single softwood pulp, and the final result shows that the tear resistance is limited; the ratio of comparative plastic paper 2# softwood pulp to hardwood pulp is outside the range defined herein, and the end result shows that the tear resistance is generally good.
The final result shows that the tear resistance is poor due to the fact that the unmodified polylactic acid fibers are used in the comparative plastic paper 3# and the analysis is due to the fact that the compatibility of the unmodified polylactic acid fibers with wood pulp and other materials and the binding force between the fibers are poor, so that the tear strength is reduced; the final result shows that the tear resistance is general due to the poor binding capacity of the nanometer cellulose with polylactic acid and wood pulp fiber; the ratio of the modified polylactic acid fiber to the silane modified nanocellulose in the comparative plastic paper No. 5 exceeds the range defined by the application, and the final result shows that the tear resistance is general, and the analysis reasons are that the binding force and the synergistic enhancement effect of the nanocellulose and the polylactic acid fiber are insufficient; comparative plastic paper # 6 used only sodium citrate as an antioxidant and the end result indicated that it had slightly poorer tear resistance. The early-stage decomposition degree is higher, the service life requirement is difficult to meet, and the analysis reason is that sodium citrate alone cannot provide enough oxidation protection, so that the paper is easy to oxidize and degrade in long-term exposure and is easier to decompose.
The foregoing is merely exemplary of the present application, and the scope of the present application is not limited to the specific embodiments, but is defined by the claims of the present application. Various modifications and changes may be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the technical ideas and principles of the present application should be included in the protection scope of the present application.
Claims (10)
1. The tear-resistant degradable plastic paper is characterized by comprising the following raw materials in parts by weight: 80-100 parts of composite wood pulp, 5-10 parts of wet strength agent, 20-30 parts of opacifying agent, 15-30 parts of composite reinforcing agent and 2-4 parts of antioxidant;
the composite wood pulp is prepared by fluffing and pulping a softwood pulp plate and a hardwood pulp plate, and the weight ratio is (6-8): (2-4), wherein the beating degree of the composite wood pulp is 25-45 DEG SR.
2. The tear-resistant degradable plastic-substituted paper according to claim 1, wherein the composite reinforcing agent comprises modified polylactic acid fibers and silane modified nanocellulose in a weight ratio of 1: (2-4).
3. The tear-resistant degradable plastic-substituted paper according to claim 2, wherein the modified polylactic acid fiber is prepared by reacting polylactic acid fiber with a grafting compatilizer and a catalyst after being subjected to plasma treatment, and the weight ratio of the polylactic acid fiber, the grafting compatilizer and the catalyst is (8-10) in sequence: (0.5-1): (0.05-0.2).
4. The tear resistant degradable plastic substituted paper of claim 3, wherein the grafting compatibility agent is ethylene oxide or glycerol monomethyl ether, and the catalyst is one of sodium hydroxide, triethylamine and dimethylaniline.
5. The tear-resistant degradable plastic substitute paper according to claim 2, wherein the preparation method of the silane modified nanocellulose is that a silane coupling agent is added into nanocellulose suspension, and the silane modified nanocellulose is obtained after stirring for uniform reaction for 2-4 hours, centrifuging and drying.
6. The tear resistant degradable plastic substituted paper according to claim 1, wherein the antioxidants are sodium citrate and benzamide in a weight ratio of 1: (0.3-0.8).
7. The tear resistant degradable plastic substituted paper according to claim 1, wherein the opacifier is an acrylic emulsion or a styrene-acrylate emulsion.
8. The tear resistant degradable plastic substituted paper of claim 1, wherein the wet strength agent is one of urea formaldehyde resin, melamine formaldehyde resin or polyamide epichlorohydrin resin.
9. A method for preparing the tear-resistant degradable plastic substituted paper according to any one of claims 1 to 8, comprising the steps of:
(1) Fluffing the softwood pulp plate and the hardwood pulp plate, and pulping by a pulping machine;
(2) And adding the composite reinforcing agent, stirring uniformly, adding the opacifier, the wet strength agent and the antioxidant, stirring uniformly, and then entering a paper machine to manufacture the tear-resistant degradable plastic substitute paper.
10. The preparation method according to claim 9, wherein the mass concentration of the fluffing slurry in the step (1) is 4-6%, and the fluffing time is 30-40min; in the step (2), the stirring speed is 200-300rpm, and the mixture is stirred for 15-30min after adding the composite reinforcing agent, and the stirring speed is 80-150g/m 2 Is quantitatively manufactured.
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