CN115125761B - Modified gelatin for papermaking reinforcing agent and preparation method and application thereof - Google Patents
Modified gelatin for papermaking reinforcing agent and preparation method and application thereof Download PDFInfo
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- CN115125761B CN115125761B CN202110325838.8A CN202110325838A CN115125761B CN 115125761 B CN115125761 B CN 115125761B CN 202110325838 A CN202110325838 A CN 202110325838A CN 115125761 B CN115125761 B CN 115125761B
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- 108010010803 Gelatin Proteins 0.000 title claims abstract description 148
- 229920000159 gelatin Polymers 0.000 title claims abstract description 148
- 235000019322 gelatine Nutrition 0.000 title claims abstract description 148
- 235000011852 gelatine desserts Nutrition 0.000 title claims abstract description 148
- 239000008273 gelatin Substances 0.000 title claims abstract description 144
- 239000012744 reinforcing agent Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 72
- 239000000839 emulsion Substances 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000011248 coating agent Substances 0.000 claims abstract description 22
- -1 polysiloxane Polymers 0.000 claims abstract description 22
- 238000000576 coating method Methods 0.000 claims abstract description 21
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 19
- 239000004593 Epoxy Substances 0.000 claims abstract description 17
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 14
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 13
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 13
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000012528 membrane Substances 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229960000583 acetic acid Drugs 0.000 claims description 7
- 239000012362 glacial acetic acid Substances 0.000 claims description 7
- 239000007764 o/w emulsion Substances 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229940083575 sodium dodecyl sulfate Drugs 0.000 claims description 3
- 239000003995 emulsifying agent Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 24
- 239000004816 latex Substances 0.000 description 20
- 229920000126 latex Polymers 0.000 description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 18
- 239000000523 sample Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 230000000694 effects Effects 0.000 description 10
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 9
- 102000008186 Collagen Human genes 0.000 description 9
- 108010035532 Collagen Proteins 0.000 description 9
- 229920001436 collagen Polymers 0.000 description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000003917 TEM image Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000002699 waste material Substances 0.000 description 7
- 108090000765 processed proteins & peptides Proteins 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000001069 Raman spectroscopy Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000003623 enhancer Substances 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- 108090000623 proteins and genes Proteins 0.000 description 5
- 102000004169 proteins and genes Human genes 0.000 description 5
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000010985 leather Substances 0.000 description 4
- 229920001184 polypeptide Polymers 0.000 description 4
- 102000004196 processed proteins & peptides Human genes 0.000 description 4
- 150000001413 amino acids Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000007385 chemical modification Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000000879 optical micrograph Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 238000004627 transmission electron microscopy Methods 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000000269 nucleophilic effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000003913 Coccoloba uvifera Nutrition 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- 240000008976 Pterocarpus marsupium Species 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- YGHUUVGIRWMJGE-UHFFFAOYSA-N chlorodimethylsilane Chemical compound C[SiH](C)Cl YGHUUVGIRWMJGE-UHFFFAOYSA-N 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000001046 green dye Substances 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000010551 living anionic polymerization reaction Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000005373 porous glass Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000011041 water permeability test Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H1/00—Macromolecular products derived from proteins
-
- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
-
- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/59—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon
-
- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
- D21H17/74—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic and inorganic material
-
- 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
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paper (AREA)
Abstract
The invention belongs to the field of gelatin application, and in particular relates to modified gelatin for a papermaking reinforcing agent, a preparation method and application thereof, wherein the modified gelatin is prepared by modifying gelatin by using epoxy polysiloxane (PDMS-E) emulsion drops, the average particle size of the epoxy polysiloxane emulsion drops is 280-450 nm, and the mass ratio of the gelatin to the PDMS-E is 1:0.75 to 0.76; the viscosity of the modified gelatin is 1.20-1.25 mPas, the conversion rate of primary amino groups in the gelatin is 7-8 mol percent, and the consumption of epoxy groups in PDMS-E is 8-10 mol percent. The invention uses monodisperse PDMS-E emulsion particles to modify gelatin, and changes the viscosity of the modified gelatin by controlling the particle size of the PDMS-E emulsion particles; solves the problems of poor hydrophobicity, poor water resistance, high viscosity, difficult coating and the like existing when the gelatin is used for the papermaking reinforcing agent.
Description
Technical Field
The invention belongs to the field of gelatin application, and relates to modified gelatin for a papermaking reinforcing agent, and a preparation method and application thereof.
Background
China is the largest leather producing country in the world, millions of tons of chrome-containing leather crushed aggregates waste are generated each year, and the waste of the waste is extremely waste of resources, and simultaneously brings great pressure to leather industry and environment. Therefore, how to effectively utilize these wastes is a problem to be solved. The waste contains a large amount of collagen, the collagen has the advantages of unique fibrous structure, good degradability, biocompatibility, film forming property and the like, and a large amount of amino, carboxyl and other active groups in the collagen molecule are easy to act with paper fibers.
Because gelatin is a polypeptide chain composed of alpha-acids through peptide bonds, each peptide chain of gelatin has a plurality of acidic or basic side groups and each peptide chain of gelatin has alpha-carboxyl alpha-amino groups at both ends, and all the groups have the capability of accepting or donating protons. The fiber is provided with a large number of hydroxyl groups, a small number of carboxyl groups and other groups, so that gelatin and the fiber can be combined through ionic bonds and covalent bonds, the bond formation of the bonds enables the bonding force between the paper-forming fibers to be increased, the bond energy to be increased, and the physical strength of paper is improved. The addition of gelatin can raise the strength of paper and has influence on the water absorption, air permeability and tightness of paper. The bonding force between fibers can be increased by adding a proper amount of gelatin. However, gelatin has its use in papermaking greatly limited by its fatal disadvantages of weak ionic properties, poor water resistance, low mechanical strength, etc. The effect of the reinforcing agent alone is not obvious and chemical modification thereof is required. If gelatin itself is grafted with more carboxyl groups or amino groups, isoelectric point transfer is performed, so that the application range is wider, and the enhancement effect is more obvious.
In the prior art, the use of gelatin in papermaking sizing agents has been reported. Chinese patent document CN110256651A (201910419833.4) adopts solvation-free waterborne polyurethane to modify collagen, uses hydrolyzed protein of waste containing chrome skin particles generated in the leather production process as raw material to prepare the papermaking function sizing agent, and solves the problem of high cost of single polyurethane. However, the contact angle of the modified gelatin sizing agent obtained by the method is 102 degrees, and the hydrophobic effect is not strong enough; the modification step is complex, and various devices are needed; the modified gelatin is large, and the problems of difficult coating or uneven coating exist when the modified gelatin is used for coating the surface of paper. Chinese patent document CN104628970a (201510039181.3) adopts a method of introducing a hydrophobic monomer into collagen, and modifies the collagen to enhance its water resistance and mechanical strength. However, the patent uses a large amount of oily acrylic acid monomer (acrylic ester, styrene, alkyl methacrylate and the like) to carry out hydrophobic modification by in-situ copolymerization with collagen, and because collagen hydrolysate is hydrophilic, a large amount of self-polymers formed by the acrylic acid oily monomer are often present, so that the grafting copolymerization rate with collagen polypeptide molecular chains is low, the copolymerization uniformity is poor, the phase separation degree is high, the film forming quality is brittle, the water resistance and the mechanical strength are poor, and the like, and the industrialization difficulty is high.
When gelatin is used as a papermaking reinforcing agent, the grafting ratio of carboxyl or amino is precisely controlled by chemical modification, and the viscosity at room temperature is controlled to be lower than 100 mPas. It can be seen that the modified gelatin does not meet the use requirements and effects of gelatin as a papermaking enhancer.
Disclosure of Invention
In order to solve the problems of poor hydrophobicity, poor water resistance, high viscosity, difficult coating and the like when the gelatin is used for a papermaking reinforcing agent, the invention provides modified gelatin for the papermaking reinforcing agent, and a preparation method and application thereof.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a modified gelatin for a papermaking reinforcing agent, characterized in that gelatin is modified by using epoxy polysiloxane (PDMS-E) emulsion droplets, wherein the average particle size of the epoxy polysiloxane emulsion droplets is 280-450 nm, and the mass ratio of the gelatin to the PDMS-E is 1:0.75 to 0.76; the viscosity of the modified gelatin is 1.20-1.25 mPas, the conversion rate of primary amino groups in the gelatin is 7-8% (mol percent), and the consumption of epoxy groups in PDMS-E is 8-10% (mol percent).
Preferably, the modified gelatin molecule has a secondary structure and a specific content of: 24-28% of alpha-helical structure; beta-sheet 23-27%; beta-rotation angle 19.5-20%; random coil 29-30%.
Further preferably, the modified gelatin molecule secondary structure and specific content are: 24.64 to 27.06 percent of alpha-helical structure; beta-sheet 23.66-26.54%; beta-rotation angle 19.61-19.73%; 29.09 to 29.67 percent of random coil. The microcosmic appearance is that part of latex particles are regular and uniform, and part of latex particles are aggregated into clusters, so that the emulsion has higher viscosity.
Preferably, the molecular weight (Mw) of the gelatin is about 1.40X105 g/mol and the Mw/Mn is 1.43. The primary amino group content in gelatin was 4.95X10 -4 g mol -1 。
The invention adopts grafted PDMS-E emulsion drop modified gelatin, which not only can keep main properties of main chain of gelatin matrix, but also can obtain new properties from grafted side chain. The invention utilizes the epoxy polysiloxane to carry out grafting reaction with the good coating agent gelatin to form the good reinforcing agent which can be used for paper, and can also improve the waterproof effect of the paper.
The preparation method of the modified gelatin comprises the following steps:
(1) Synthesis of Mono Si-H terminated polysiloxane (PDMS-H): with hexamethylcyclotrisiloxane (D) 3 ) Is monomer, n-butyllithium (C) 4 H 9 Li) as initiator, benzene as solvent, tetrahydrofuran (THF) as accelerator, dimethyl-hydrosilyl-chlorane (C) 2 H 7 ClSi) as a capping agent, and synthesizing PDMS-H using living anionic polymerization techniques;
the reaction equation:
making n in the process be 6-14;
(2) Preparation of epoxy polysiloxane (PDMS-E): under the action of a catalyst chloroplatinic acid, performing hydrosilylation reaction on Allyl Glycidyl Ether (AGE) and PDMS-H to obtain epoxy polysiloxane (PDMS-E);
the reaction equation is:
(3) Preparation of monodisperse PDMS-E emulsion particles:
PDMS-E is taken as a disperse phase, passes through the membrane pores of an SPG membrane emulsifier under the pressure of nitrogen, and is added into deionized water containing Sodium Dodecyl Sulfate (SDS), sodium Dodecyl Benzene Sulfonate (SDBS) and glacial acetic acid to form PDMS-E oil-in-water emulsion;
(4) The monodisperse PDMS-E emulsion particles react with gelatin to modify the gelatin: and (3) regulating the pH value of the gelatin solution to 10.0+/-0.2, dropwise adding the PDMS-E emulsion prepared in the step (3) into the gelatin solution, and stirring to obtain the monodisperse PDMS-E emulsion particle modified gelatin.
Preferably, the specific method of the step (1) is as follows: first C is carried out 4 H 9 Li is dissolved in benzene, D dissolved in benzene is added under the condition of decompressing and introducing argon 3 After a period of reaction, THF is added for a period of time, and then C is injected 2 H 7 Stopping the reaction after ClSi; the product was then filtered, distilled under reduced pressure and purified to give PDMS-H.
Further preferably, D 3 /C 4 H 9 Li/C 2 H 7 The molar ratio of ClSi is 1.9-2.1:3.9-4.1:1.
Further preferably, C 4 H 9 The volume of Li is 2.3 to 2.5 times that of benzene; the volume of THF is 4.8-5.2 times that of benzene.
Further preferably, D is added 3 Post-reaction for 28-32 min; after THF is added, the reaction is continued for 7.5 to 8.5 hours.
Preferably, the specific method of the step (2) is as follows: argon is introduced into the AGE, and chloroplatinic acid is added after 25 to 35 minutes; heating to 78-82 ℃, dropwise adding PDMS-H, heating to 108-112 ℃ after the dropwise adding, reacting for 5.5-6.5H, and purifying the product by reduced pressure distillation to obtain the product epoxy polysiloxane (PDMS-E).
Further preferably, the mass ratio of AGE to chloroplatinic acid is 1: 0.011-0.012.
It is further preferred that the molar ratio of PDMS-H to AGE is 1.5 to 1.7:1.
Preferably, in step (3), the SDS/SDBS ratio (w/w) is 0.25-0.3, and the total concentration of the surfactant in the deionized water is 0.25-0.3 wt%.
Preferably, in step (3), the SPG membrane has an average pore size of 0.5 μm.+ -. 0.1.
Preferably, in the step (3), the concentration of glacial acetic acid in the deionized water is 2-3 mol/L.
Preferably, in the step (3), the mass fraction of PDMS-E in the oil-in-water emulsion is 0.95-1.05%.
Preferably, the specific method of the step (4) is as follows:
dissolving gelatin in distilled water to prepare gelatin solution, and heating the gelatin solution to 49-51 ℃ after 2.5-3.5 h to ensure that gelatin is completely dissolved; subsequently, the pH of the gelatin solution was adjusted to 10.0.+ -. 0.2 using sodium hydroxide solution; then, the PDMS-E emulsion prepared in the step (3) is mixed with the water according to the proportion of 19-21 mL.min -1 Is added to the gelatin solution and stirred at 49-51 c for 5-6 hours.
It is further preferred that the concentration of the sodium hydroxide solution in the step (4) is 1.8 to 2.2mol L -1 。
It is further preferred that the mass percentage of gelatin in the gelatin solution in step (4) is 4.95 to 5.05wt%.
The invention also provides application of the modified gelatin in papermaking.
Preferably, the present invention provides the use of the modified gelatin described above as a papermaking enhancer.
The invention also provides a paper with enhanced mechanical strength, which contains the modified gelatin, wherein the coating amount of the modified gelatin is 0.1mL/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The tensile strength of the paper is 26-36 MPa, and the elongation at break is 10-40%;
preferably, the paper base has the following index: the quantitative amounts were (16.0.+ -. 2.2) to (50.0.+ -. 2.5) g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The tensile strength is 1-20 Mpa; the elongation at break is 7-37%; the water content is 5.8-6.2%.
The basis weight of the paper is preferably 16-50 g/m 2 。
Preferably, the paper base is writing paper, copying paper or crepe soft paper.
Further preferably, the specific application method of the modified gelatin as a reinforcing agent in papermaking is as follows:
after the pulp is made into the formed paper, the reinforcing agent is uniformly coated on the paper stock and dried for 24 hours at room temperature. The modified gelatin can be used as a reinforcing agent in papermaking to improve the toughness, water resistance and physical strength of paper.
The invention has the following technical effects:
epoxy polysiloxanes are polymers with low glass transition temperatures, low surface energies, superhydrophobicity, oxidation resistance, and excellent elasticity and breathability. Under alkaline conditions, the epoxy groups in the epoxysilicone can react with primary amino groups in the protein in a ring-opening way, so that the silicone chain segment and the polypeptide molecule are connected through a C-N covalent bond, and the epoxysilicone chain segment can be grafted on the polypeptide molecule. The low surface of the polysiloxane chain segment promotes the migration of molecules to the surface, and can endow the material with super-hydrophobic property, high and low temperature resistance, flexibility, radiation resistance and air permeability. However, epoxypolysiloxanes are oily polymers and gelatin is water soluble, and the reaction of the two is difficult to control.
The invention uses monodisperse PDMS-E emulsion particles to modify gelatin, and changes the viscosity of the modified gelatin by controlling the particle size of the PDMS-E emulsion particles. In addition, the single PDMS-E latex particles have the characteristics of uniform shape, structure and size, and uniform distribution of surface functional groups, and are uniformly distributed in the emulsion when chemical modification is performed, so that chemical reaction is more sufficient, and the reaction conditions can be accurately regulated and controlled.
The particle size of the emulsion particle modified gelatin is 280-450 nm, and the viscosity is 1.20-1.25 mPas; solves the problems of poor hydrophobicity, poor water resistance, high viscosity, difficult coating and the like existing when the gelatin is used for the papermaking reinforcing agent.
Drawings
FIG. 1 is an optical microscope image and particle size distribution diagram of monodisperse emulsion particles of example 1;
FIG. 2 is an optical microscope image and particle size distribution diagram of monodisperse emulsion particles of example 2;
FIG. 3 is an optical microscope image and a particle size distribution diagram of monodisperse emulsion particles of comparative example 1;
FIG. 4 is a graph of the microtopography of the modified gelatin of example 1;
FIG. 5 is a graph of the micro-morphology of the modified gelatin of comparative example 1;
fig. 6 is a graph of the wetting effect of different modified gelatins as paper making enhancers.
Detailed Description
The invention is further illustrated and described below with reference to the drawings and examples.
Sodium Dodecyl Sulfate (SDS), sodium Dodecyl Benzene Sulfonate (SDBS), allyl Glycidyl Ether (AGE) and glacial acetic acid are all available from Alfa Aesar (Alfa Aesar) Inc. of Shanghai China and SDS and SDBS require recrystallization from ethanol prior to use. Hexamethylcyclotrisiloxane (D) 3 ) N-butyllithium (C) 4 H 9 Li) and chlorodimethylsilane (C) 2 H 7 ClSi) was purchased from Sigma Aldrich. Benzene and Tetrahydrofuran (THF) were purchased from chinese pharmaceutical groups company (beijing). SPG porous glass membranes with pore size of 0.5 μm were purchased from China medical group company. Chloroplatinic acid was purchased from atanan platinum source chemical company, inc; pigskin A gelatin is purchased from China medical group company, and is used after dialysis.
Molecular weight of gelatin (M) as determined by gel permeation chromatography w ) About 1.40×10 5 g mol -1 ，M w /M n 1.43. The primary amino group content of gelatin was measured by Van-Slike method at 50℃and found to be 4.95X10 -4 g mol -1 . Van-Slike method is a specialized method for determining the amino content of amino acids or protein molecules. The method is to determine the primary amino content in amino acid or protein by reacting nitrous acid with the primary amino in amino acid or protein. The error in primary amino content in gelatin measured using this method is less than 1%.
The physical size of the emulsion droplets and the Polymer Dispersion Index (PDI) were measured with a laser particle size analyzer (Zetasizer 2000, malvern instruments, uk). The instrument converts the diffraction spectrum into a particle size distribution curve based on Mie scattering theory. First, the emulsion was carefully placed into a color matching tube. The tube was then placed in a ZetaSizer 2000 laser particle meter to measure PDI or electrophoretic mobility.
The viscosity of the sample in the reaction liquid at different time is measured by using a black-bone viscometer, the constant temperature tank is adjusted to 50 ℃, the black-bone viscometer is vertically placed in the constant temperature tank, 15mL of the sample to be measured is taken and added into the viscometer, the two pipes except the capillary are sealed, the liquid level is pumped to the upper scale mark of the glass ball at the upper end of the capillary by using an air pumping device, meanwhile, the air pumping device is removed, and the time required for the liquid level to flow down from the upper scale mark to the lower scale mark is recorded, so that the viscosity is calculated.
Raman spectra of reaction samples in the reaction solutions at different times were recorded with a raman spectrometer, raman spectral data were measured using an inVia type (Renishaw, uk) laser confocal raman spectrometer, first focused on the capillary surface using an optical microscope mode, stage focused on the particle surface was adjusted, and raman spectral data were obtained using a 633nm laser source. The consumption of epoxy groups is detected by Raman spectroscopy, 858cm -1 The peak represents an epoxy group.
The Zeta potential of the reaction sample in the reaction liquid at different times is measured by a Zetasizer Nano ZS type (Malvern, UK) laser particle sizer, the sample is sucked by a syringe and slowly injected into a cuvette with the Zeta potential, and a specific Zeta potential value can be measured by putting the cuvette into a sample tank of the instrument without bubbles. The experimental results were repeated 3 times.
The morphology of PDMS-E latex particles was characterized by Transmission Electron Microscopy (TEM). First, a TEM sample was prepared. The mixture of gelatin and emulsion was diluted about 20-fold at 50 ℃. The drop-like mixture was dropped onto the copper mesh. The excess liquid was absorbed by filter paper and dried with nitrogen at room temperature. TEM images were measured with JEM-2100.
The synthetic method of the epoxy polysiloxane (PDMS-E) used in the embodiment of the invention is as follows:
(1) Synthesis of Mono Si-H terminated polysiloxane (PDMS-H):
first 10mL of benzene was added to the flask, followed by 24mL of C 4 H 9 Li, 45.99 g of D after 3-5 times of vacuumizing and argon introducing operations 3 Dissolved in 40mL benzene and added dropwise to the flask. After 30min of reaction, 50mL of Tetrahydrofuran (THF) was added and the reaction was continued for 8h. Subsequently, 11mL of C 2 H 7 ClSi was injected into the flask to terminate the reaction. The obtained product PDMS-H is purified by filtration, reduced pressure distillation and the like, and 45.44g of the product is obtained, and the yield is 56.11%. D (D) 3 /C 4 H 9 Li/C 2 H 7 The molar ratio of ClSi is about 2:4:1.
(2) Preparation of epoxy polysiloxane (PDMS-E): 8.51g of AGE was charged into the flask, and after 30 minutes, 40. Mu.L of chloroplatinic acid (mass of chloroplatinic acid: 0.097 g) was added thereto. And under the condition of keeping argon gas, the reaction temperature is increased to 80 ℃, PDMS-H with the molar ratio of 1.6:1 with AGE is added at the speed of 1-2 d/s, after the dropwise addition is finished, the reaction temperature is continuously increased to 110 ℃, the reaction is continued for 6 hours, and then the reaction is finished. The product epoxy polysiloxane (PDMS-E) is obtained through purification by means of reduced pressure distillation and the like, and the yield is 84.32%.
Example 1
A modified gelatin for papermaking reinforcing agent, which is prepared by the following steps:
(1) Preparation of monodisperse PDMS-E emulsion particles:
PDMS-E was used as the dispersed phase, and was passed through SPG membrane pores (average pore diameter of SPG membrane 0.5 μm) under nitrogen pressure, added to deionized water (glacial acetic acid concentration 2 mol/L) containing SDS, SDBS and glacial acetic acid, and stirred at a rotation speed of 1300rpm to form PDMS-E oil-in-water emulsion (PDMS-E mass percentage in oil-in-water emulsion 1%). The SDS/SDBS ratio (w/w) was 0.25 and the total concentration of surfactant in deionized water was 0.3wt%.
(2) The monodisperse PDMS-E emulsion particles react with gelatin to modify the gelatin:
the stock solution was prepared by dissolving gelatin in distilled water (5 wt%) and after 3 hours the gelatin solution was heated to 50 ℃ to ensure complete dissolution of gelatin. Subsequently, the pH of the gelatin solution was adjusted to 10.0.+ -. 0.2 using sodium hydroxide solution (NaOH, 2.0 mol/L). Then, the PDMS-E emulsion particles prepared above were added to the gelatin solution at a rate of 20mL/min and stirred at 50℃for 5 hours. Mass ratio of PDMS-E to gelatin 0.757:1. to obtain the monodisperse PDMS-E latex particle modified gelatin with the viscosity of 1.25 mPas.
The average particle diameter of the epoxy polysiloxane obtained in example 1 was 366.+ -.70 nm (shown in FIG. 1), and it can be seen from TEM image (FIG. 4) that the modified gelatin latex particles were aggregated.
The conversion of primary amino groups in gelatin was 7.5% (mole percent) and the epoxy group consumption in PDMS-E was 8.5% (mole percent).
Example 2
A modified gelatin for papermaking reinforcing agent, which is prepared by the following steps:
otherwise, the same as in example 1 was changed to SDS: SDBS 0.3 and total surfactant concentration 0.25 wt.% to obtain monodisperse emulsion particles with particle size of 392+ -40 nm (figure 2), and then modifying gelatin. The conversion of primary amino groups in gelatin was 7.8% (mole percent); the epoxy group consumption in PDMS-E was 9.2% (mole percent); the viscosity was 1.20 mPas.
Comparative example 1
A modified gelatin, the preparation method:
other than the same as in example 1, the average pore diameter of the SPG membrane was 0.7. Mu.m, SDS was changed: SDBS was 0.67 and the total surfactant concentration was 0.5wt%. Monodisperse PDMS-E latex particle modified gelatins with a viscosity of 1.057mPas were obtained. The particle size of the obtained epoxy polysiloxane emulsion drops is 955+/-70 nm; the morphology was a uniformly distributed multi-layer structure (shown in FIG. 5), the primary amino conversion in gelatin was 13.73% (mole percent), and the epoxy consumption in PDMS-E was 27.27% (mole percent). .
1. The particle sizes of the obtained monodisperse PDME-S emulsion particles with different particle sizes
The size of the latex particles produced was described by mean particle size and dispersion index (PDI), which indicated that the PDI of the emulsion particles was less than 0.1, indicating that the emulsion particles were uniformly distributed in the solution. Particle size variation Coefficient (CV) of less than 21% also indicates a sufficiently narrow particle size distribution. The monodisperse PDME-S latex particles are suitable for modifying gelatin to obtain the modified gelatin with stable performance.
The particle size of the modified gelatin under the optical microscope and the particle size of the modified gelatin under the TEM are somewhat different because: the latex particles under the optical microscope are detected in the latex, the particle size is consistent with the actual particle size result, and the modified gelatin particles in the TEM image can collapse and shrink to a certain extent after being subjected to treatment such as dripping on a copper mesh (carbon support film) and moisture drying during testing. The size of the modified gelatin in the TEM image is smaller than the particle size of the latex particles, and the reason why some of the latex particles in the TEM image are not significantly spherical is that the TEM image is merely for observing the microstructure, and is not for reflecting the size of the modified gelatin particle size in the actual application state.
The reaction of gelatin with PDMS-E latex particles is affected by a number of factors, the morphology of which is also very complex. The TEM image (figures 4 and 5) can intuitively observe the latex particle modified gelatin with small particle size less than about 400nm, and the latex particles are regular and uniform and partially aggregated to form a cluster, so that the emulsion has higher viscosity. The size is small, the surface is easier to contact and adsorb on the surface, the grafting rate can ensure that gelatin and latex particles are grafted and a part of monomers can be ensured to play a role in adhesion.
Whereas larger size monodisperse latex particles exhibit a multi-layer structure, this may be due to the fact that gelatin can give ordered colloidal aggregates when nucleophilic attack occurs on the surface of the latex particles. While for smaller droplets, collapse of the droplet, nucleophilic attack and complex formation occur simultaneously.
The particle size, the secondary structure, the grafting rate and other reasons affect the performance of the modified gelatin together, so that different modified gelatins have different characteristics and application prospects.
2. Secondary structure content of modified gelatins of different examples and comparative examples
TABLE 1
The proportion of alpha-helix and random coil in the secondary structure of the emulsion with small particle size is more, so that the viscosity of the emulsion is higher, the gelatin is distributed more uniformly in the emulsion, the gelatin is not concentrated near latex particles, the film formation is easier, the viscosity and the strength are higher, and the emulsion is more advantageous for paper reinforcing agents. The modified gelatin provided by the invention has the advantages that the emulsion particle is between 280 and 450nm, the viscosity is between 1.15 and 1.25mPas, the viscosity change range of the modified gelatin is narrow, the stability is good, better adhesive effect can be provided, and the viscosity of the modified gelatin is proper, so that uniform coating is not influenced greatly.
3. Modified gelatin emulsion as papermaking reinforcing agent
To test the effect of the modified gelatin of the present invention on paper properties for use as a papermaking enhancer, a plain tissue was selected as the test subject. Tissues were prepared as substrates to 10X 10mm of the same size. The emulsion was then dropped onto a substrate (plain paper towel) with a dropper (the drop amount was 0.1mL/cm, calculated on the surface area of the paper) 2 ) The distance between the base material and the dropper is kept about 5cm, after the modified gelatin is uniformly dripped or sprayed on the surface of the base material by using a spray gun, the base material and the dropper are preserved for 12 hours at room temperature, and a test paper sample is obtained.
Characterization of the coating: the water contact angle was measured with the contact angle (SL 250 USA KINO Industry). The paper samples were adhered to a very small glass plate to avoid curling of the paper and the water contact angle was measured with deionized water.
Wettability test: the paper sample was placed on a filter paper and deionized water with an acidic fruit green dye was dropped onto the sample. The state of the sample and filter paper at different time points was observed and recorded.
As shown in fig. 6, the blank is a paper towel without any coating, and the results of the water permeability test show that the soft absorbent paper has a super hydrophilic interface (contact angle <5 °) and that water drops rapidly spread on the absorbent paper without any coating. And after the modified gelatin product made of emulsion with different sizes is coated on paper, the water-resistant permeability of the coating is obviously improved along with the increase of the size of emulsion particles, and the hydrophobic interface (CA >120 degrees) of the paper is displayed.
For the modified gelatin coating sample of comparative example 1, the water droplets had significant permeability after 60 minutes; whereas for the modified gelatin coating samples of examples 1-2, the water droplets hardly had permeability, probably because of the poor grafting ratio, more PDMS-E dispersed in the emulsion, and the like, so that PDMS-E as an active ingredient can be uniformly distributed in the paper.
The modified gelatin provided by the invention can be used as a papermaking reinforcing agent, so that the viscosity of the gelatin can be reduced, the gelatin can be conveniently coated into a uniform coating, and meanwhile, the coating is endowed with a hydrophobic and water-resistant effect.
To illustrate the effect of modified gelatin as a paper reinforcing agent on paper base, the tensile strength of paper samples was tested using a microcomputer controlled electronic universal tester.
Example 3: paper with enhanced mechanical strength, wherein the paper base is writing paper: national standard GB12654-90, quantitative 50.0g/m 2 Tensile strength 12.09MPa, elongation at break 7.4%; EXAMPLE 1 coating amount of modified gelatin was 0.1mL/cm 2 。
Example 4: paper with enhanced mechanical strength, the paper base is copy paper: GB1911-91 with a basis weight of 19.0g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the Tensile strength 19.38MPa; elongation at break 7.3%, coating weight of modified gelatin of example 1 was 0.1mL/cm 2 。
Example 5: a paper with enhanced mechanical strength is a creped soft paper (ZBY, 39001-88, basis weight 16.0g/m 2 ) The method comprises the steps of carrying out a first treatment on the surface of the Tensile strength 1.83MPa; elongation at break 36.3%, coating weight of modified gelatin of example 1 was 0.1mL/cm 2 。
Comparative example 2: paper with enhanced mechanical strength, the paper base is xerographic paper: national standard ZBY32004-86, quantitative 70.0g/m 2 The modified gelatin of example 1 was applied in an amount of 0.1mL/cm with a tensile strength of 18.65MPa and an elongation at break of 8.9% 2 。
The various sample papers of examples 3 to 5 and comparative example 2 were prepared as substrates to 10X 10mm of the same size. Then the prepared modified gelatin (example 1) was dropped on the upper surface of the corresponding paper with a dropper in an amount of 0.1mL/cm 2 Keeping a distance of about 5cm between the base material and the dropper, and preserving at room temperature for 12 hours to obtain a test paper sample, namely a modified sample.
ComparisonExample 3 and comparative example 4 are modified writing papers using the modified gelatin obtained in example 1 as a reinforcing agent, unlike example 3, comparative example 3 and comparative example 4 adjust the amounts of the modified gelatin to 0.05mL/cm, respectively 2 And 0.15mL/cm 2 。
Tensile strength and elongation at break were tested and the results are shown in table 2:
TABLE 2
| Sample name | Tensile strength (MPa) | Elongation at break% |
| Example 3 | 31.29 | 10.4 |
| Example 4 | 35.68 | 10.9 |
| Example 5 | 26.17 | 36.9 |
| Comparative example 2 | 22.25 | 9.3 |
| Comparative example 3 | 17.12 | 8.2 |
| Comparative example 4 | 30.25 | 6.8 |
As can be seen, the amount of modified gelatin used as an enhancer was 0.1mL/cm 2 The effect is optimal. When the paper base is electrophotographic paper, the reinforcing effect of tensile strength and elongation at break is not obvious.
From the data, the tensile strength of the modified samples is generally improved compared with that of the blank samples, which indicates that the coating can increase the strength of the paper.
Claims (8)
1. The paper with enhanced mechanical strength is characterized in that the tensile strength of the paper is 26-36 MPa, and the elongation at break is 10-40%; the coating weight of the modified gelatin on the paper base surface was 0.1mL/cm 2 ；
The modified gelatin is as follows:
modifying gelatin by using monodisperse epoxy polysiloxane (PDMS-E) emulsion drops, wherein the average particle size of the epoxy polysiloxane emulsion drops is 280-450 nm, and the mass ratio of the gelatin to the PDMS-E is 1:0.75-0.76; the viscosity of the modified gelatin is 1.20-1.25 mPas, the conversion rate of primary amino groups in the gelatin is 7-8 mol percent, and the consumption of epoxy groups in PDMS-E is 8-10 mol percent;
preparation of monodisperse PDMS-E emulsion droplets:
PDMS-E is taken as a disperse phase, passes through the membrane pores of an SPG membrane emulsifier under the pressure of nitrogen, and is added into deionized water containing Sodium Dodecyl Sulfate (SDS), sodium Dodecyl Benzene Sulfonate (SDBS) and glacial acetic acid to form PDMS-E oil-in-water emulsion; the ratio (w/w) of SDS/SDBS is 0.25-0.3, the total concentration of the surfactant in the deionized water is 0.25-0.3 wt%, the average pore diameter of the SPG film is 0.5, the average pore diameter is surface active, and the mass fraction of PDMS-E in the oil-in-water emulsion is 0.95-1.05%;
the method for modifying the gelatin by reacting the monodisperse PDMS-E emulsion droplets with the gelatin comprises the following steps:
dissolving gelatinPreparing gelatin solution in distilled water, and heating the gelatin solution to 49-51 ℃ after 2.5-3.5 h to ensure that gelatin is completely dissolved; subsequently, the pH of the gelatin solution was adjusted to 10.0.+ -. 0.2 using sodium hydroxide solution; then, the PDMS-E emulsion is mixed with the mixture of the water and the solvent at a concentration of 19-21 mL.min -1 Is added to the gelatin solution and stirred at 49-51 c for 5-6 hours.
2. The paper with enhanced mechanical strength according to claim 1, wherein the modified gelatin molecule secondary structure and specific content are: 24-28% of alpha-helical structure; beta-sheet 23-27%; beta-rotation angle 19.5-20%; random coil 29-30%.
3. The paper of claim 1, wherein the glacial acetic acid concentration in deionized water is 2 to 3mol/L.
4. The paper with enhanced mechanical strength according to claim 1, wherein the concentration of the sodium hydroxide solution is 1.8 to 2.2mol L -1 。
5. The paper with enhanced mechanical strength according to claim 1, wherein the mass percentage of gelatin in the gelatin solution is 4.95-5.05 wt%.
6. The paper with enhanced mechanical strength according to claim 1, wherein the paper base has an index of: the ration is 13.8-52.5 g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The tensile strength is 1-20 Mpa; the elongation at break is 7-37%; the water content is 5.8-6.2%.
7. The mechanically enhanced paper of claim 1 wherein said paper substrate comprises writing paper, copy paper, creped soft paper.
8. The method for producing a paper having enhanced mechanical strength according to any one of claims 1 to 7, wherein the modified gelatin reinforcing agent is uniformly coated on the paper stock after the pulp is formed into a molded paper, and dried at room temperature for 24 hours.
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| GB343248A (en) * | 1929-01-17 | 1931-02-19 | Papeteries Navarre | |
| CN105419350A (en) * | 2015-12-22 | 2016-03-23 | 齐鲁工业大学 | Monoepoxy-blocked polysiloxane modified gelatin gradient film prepared by substrate adjusting method |
| CN110904728A (en) * | 2019-11-21 | 2020-03-24 | 陕西科技大学 | Gelatin-based papermaking sizing agent based on hydrogen bond effect and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB343248A (en) * | 1929-01-17 | 1931-02-19 | Papeteries Navarre | |
| CN105419350A (en) * | 2015-12-22 | 2016-03-23 | 齐鲁工业大学 | Monoepoxy-blocked polysiloxane modified gelatin gradient film prepared by substrate adjusting method |
| CN110904728A (en) * | 2019-11-21 | 2020-03-24 | 陕西科技大学 | Gelatin-based papermaking sizing agent based on hydrogen bond effect and preparation method thereof |
Non-Patent Citations (1)
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| Cong Zhu etc.Scale Effect on the Interface Reaction between PDMS‑E EmulsionDroplets and Gelatin.《American Chemical Society》.2017,第第33卷卷第9926-9933页. * |
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