CN116732816A - Waterproof self-adhesive papermaking auxiliary agent and preparation method and application thereof - Google Patents
Waterproof self-adhesive papermaking auxiliary agent and preparation method and application thereof Download PDFInfo
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- CN116732816A CN116732816A CN202310803900.9A CN202310803900A CN116732816A CN 116732816 A CN116732816 A CN 116732816A CN 202310803900 A CN202310803900 A CN 202310803900A CN 116732816 A CN116732816 A CN 116732816A
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- 239000012752 auxiliary agent Substances 0.000 title claims abstract description 53
- 239000000853 adhesive Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229920002635 polyurethane Polymers 0.000 claims abstract description 66
- 239000004814 polyurethane Substances 0.000 claims abstract description 66
- 239000000463 material Substances 0.000 claims abstract description 58
- 125000005375 organosiloxane group Chemical group 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 229920005862 polyol Polymers 0.000 claims description 27
- 150000003077 polyols Chemical class 0.000 claims description 27
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 17
- 239000000178 monomer Substances 0.000 claims description 16
- 125000005442 diisocyanate group Chemical group 0.000 claims description 13
- 229920006150 hyperbranched polyester Polymers 0.000 claims description 11
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 8
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000003431 cross linking reagent Substances 0.000 claims description 8
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 8
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- LEVWYRKDKASIDU-QWWZWVQMSA-N D-cystine Chemical compound OC(=O)[C@H](N)CSSC[C@@H](N)C(O)=O LEVWYRKDKASIDU-QWWZWVQMSA-N 0.000 claims description 5
- 229960003067 cystine Drugs 0.000 claims description 5
- 239000005871 repellent Substances 0.000 claims description 5
- KYNFOMQIXZUKRK-UHFFFAOYSA-N 2,2'-dithiodiethanol Chemical compound OCCSSCCO KYNFOMQIXZUKRK-UHFFFAOYSA-N 0.000 claims description 4
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 238000006482 condensation reaction Methods 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000012948 isocyanate Substances 0.000 claims description 4
- 150000002513 isocyanates Chemical class 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 10
- 239000000835 fiber Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 7
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 abstract description 5
- 230000002441 reversible effect Effects 0.000 abstract description 3
- 230000002209 hydrophobic effect Effects 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 abstract description 2
- 238000004537 pulping Methods 0.000 abstract description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 24
- 229920006264 polyurethane film Polymers 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 239000003292 glue Substances 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000000227 grinding Methods 0.000 description 6
- 238000010907 mechanical stirring Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- -1 polytetrafluoroethylene Polymers 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000001913 cellulose Substances 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 238000007731 hot pressing Methods 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000008446 instant noodles Nutrition 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004660 morphological change Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 238000004078 waterproofing 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
- D21H21/16—Sizing or water-repelling 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/04—Hydrocarbons
-
- 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
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/14—Carboxylic acids; Derivatives thereof
- D21H17/15—Polycarboxylic acids, e.g. maleic acid
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/64—Paper recycling
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The application relates to the field of pulping and papermaking auxiliary agents, in particular to a waterproof self-bonding papermaking auxiliary agent, a preparation method and application thereof. The application introduces organic siloxane and disulfide bonds with heat reversible dynamic exchange performance into polyurethane auxiliary agent, and coats the polyurethane auxiliary agent on the surface of paper-based material to prepare multifunctional paper-based material, which is not only based on the hydrophobic effect of the organic siloxane and has stronger waterproof performance, but also can lead the paper-based material to be self-bonded by utilizing the heat reversible dynamic exchange effect of the disulfide bonds in the molecular structure of the polyurethane auxiliary agent and the interpenetrating network structure between paper-based fibers under the condition of not adding any adhesive when the paper-based material is bonded and hot-pressed for molding.
Description
Technical Field
The application relates to the field of pulping and papermaking auxiliary agents, in particular to a waterproof self-bonding papermaking auxiliary agent, a preparation method and application thereof.
Background
Paper-based materials are widely used in various fields as the most representative sustainable natural green materials, playing an important role in daily life and production. In particular, in recent years, with the development of the logistics industry, the pollution problem generated by plastic packaging products is more and more concerned, and the development trend at home and abroad shows the importance and urgency of plastic limitation, which brings new opportunities for the development of paper-based packaging materials. However, the process is not limited to the above-described process,
because the cellulose surface of the natural plant fiber contains a large amount of hydroxyl groups and has stronger hydrophilicity, the paper-based material which is not subjected to any modification treatment has strong hygroscopicity, and the strength index of the paper-based material after moisture absorption is obviously reduced, so that the subsequent use performance of the paper-based material is affected. Accordingly, in order to improve the water resistance of paper-based materials, the conventional pulp and paper industry has generally employed treatments that impart liquid penetration and diffusion resistance to paper-based materials by means of internal or surface sizing. However, not only is the production process cumbersome and the drying time consuming, but also as the application of the paper-based material in various fields is gradually expanded, the traditional sizing technology can not meet the requirements of certain fields on the performance of the paper-based material. Paper straws, paper-based packaging cushioning materials and the like used in daily life require excellent waterproofing, and an adhesive is required to be added in the preparation process, so that the conventional sizing method cannot meet the use requirements of the paper-based materials.
At present, the adhesive such as pasting glue, water-based sealing glue, paper-plastic composite glue and the like are widely applied to the sealing of instant noodle boxes, the lamination of various packaging boxes, the sealing and edge sealing of the bottom sealing of handbag, the adhesion of paper and plastic PVC and the like; chinese patent CN 111154059A discloses an epoxy resin modified polyether amine reinforced waterborne polyurethane emulsion and a preparation method thereof, wherein the epoxy resin is introduced to the main chain of the waterborne polyurethane, the molecular chain structure is more regulated than that of other methods, the hydroxyl contained in the epoxy resin is not destroyed, and the bonding strength, the water resistance and the heat resistance of the waterborne polyurethane are well improved. However, when the adhesive is used, the adhesive needs to be used after the moisture in the glue is dried, the adhesive has slow effect, and the adhesive effect is greatly affected by the moisture, namely, the adhesive force is weakened or vanished under water environment. Therefore, a waterproof self-adhesive papermaking auxiliary agent is urgently needed.
Disclosure of Invention
Aiming at the problems that the waterproof adhesive in the present stage has slow effect in the preparation process and is greatly influenced by water, the waterproof self-bonding papermaking auxiliary agent provided by the application specifically introduces organic siloxane and disulfide bonds with heat reversible dynamic exchange performance into polyurethane auxiliary agent, and coats the polyurethane auxiliary agent on the surface of paper-based material to prepare the multifunctional paper-based material.
The technical scheme of the application is as follows:
the waterproof self-adhesive papermaking auxiliary agent comprises the following raw materials: a terminal dihydroxy polyol, a terminal dihydroxy organosiloxane, a terminal dihydroxy monomer containing disulfide bonds, a diisocyanate, a terminal hydroxy hyperbranched polyester;
the molar ratio of total hydroxyl groups (-OH) in the terminal dihydroxy polyol, the terminal dihydroxy organosiloxane and the disulfide bond-containing terminal dihydroxy compound to isocyanate groups (-NCO) in the diisocyanate is n (-OH): n (-NCO) =3: 4, the molar ratio of hydroxyl (-OH) in the hydroxyl-terminated hyperbranched polyester to isocyanate (-NCO) in the diisocyanate is n (-OH): n (-NCO) =1: 4.
preferably, when the terminal dihydroxy polyol and the terminal dihydroxy organosiloxane are used as the soft segments, and the terminal dihydroxy monomer containing disulfide bonds is used as the crosslinking agent, the molar ratio of the terminal dihydroxy polyol to the terminal dihydroxy organosiloxane is 0.5: 1-2: 1, the molar ratio of the whole of the terminal dihydroxy polyol and the terminal dihydroxy organosiloxane to the diisocyanato is 1:2, the mol ratio of the terminal dihydroxy monomer containing disulfide bond to the diisocyanato is 1:4.
preferably, when the terminal dihydroxy polyol and the terminal dihydroxy monomer containing disulfide bond are used as the soft segment and the terminal dihydroxy organosiloxane is used as the crosslinking agent, the molar ratio of the terminal dihydroxy polyol to the terminal dihydroxy organosiloxane is 0.5: 1-2: 1, the molar ratio of the whole of the terminal dihydroxy polyol and the terminal dihydroxy organosiloxane to the diisocyanato is 1:2, the molar ratio of terminal dihydroxy organosiloxane to diisocyanato is 1:4.
preferably, the polyalcohol is one or two of polyethylene glycol and polytetrahydrofuran, and the molecular weight of the polyalcohol is 800-5000 g/mol; and/or the diisocyanate is one or more of isophorone diisocyanate, hexamethylene diisocyanate, 4' -methylenebis (phenyl isocyanate); and/or the molecular weight of the terminal dihydroxy organosiloxane is 800-5000 g/mol; and/or the terminal dihydroxy monomer containing disulfide bond is one or more of cystine, bis (2-hydroxyethyl) disulfide and 2, 2-diaminodiphenyl disulfide; and/or the hydroxyl number of the terminal hydroxyl-terminated hyperbranched polyester can be 8, 12, 24, 36 and 48, and the corresponding molecular weight is 800-5000 g/mol.
The application also provides a preparation method of the waterproof self-adhesive papermaking auxiliary agent, which comprises the following steps:
s1, performing condensation reaction on terminal dihydroxy polyol, terminal dihydroxy organosiloxane and diisocyanate under the action of a catalyst dibutyl tin dilaurate to synthesize an isocyanate-terminated polyurethane prepolymer;
s2, adding hydroxyl-terminated hyperbranched polyester into a reaction system S1, and preparing hyperbranched polyurethane through condensation reaction of hydroxyl in the molecular structure of the hydroxyl-terminated hyperbranched polyester and isocyanate residual in the S1;
s3, adding a terminal dihydroxy monomer containing disulfide bonds into the S2 reaction system, and crosslinking different hyperbranched polyurethanes together by utilizing the reaction between hydroxyl groups at two ends of the compound and residual isocyanate groups in the polymerization reaction to synthesize the polyurethane auxiliary agent with higher crosslinking degree.
Further, the terminal dihydroxy organosiloxane of step S1 is interchanged with the disulfide bond-containing terminal dihydroxy monomer of step S3.
Further, the reaction temperature in the step S1 is 40-80 ℃ and the reaction time is 3-8 h.
Further, the reaction temperature in the step S2 is 30-50 ℃ and the reaction time is 3-6 h; and/or the reaction temperature in the step S3 is 30-50 ℃ and the reaction time is 3-6 h.
Another object of the application is the use of a protective water-repellent self-adhesive papermaking aid as a water-repellent layer for paper.
The specific process of the application is that the obtained auxiliary agent is coated on paper-based materials and hot pressed.
The synthetic route of the matrix is shown in fig. 1 and 2, and fig. 1 is a synthetic route of the papermaking auxiliary agent which takes terminal dihydroxy polyol and terminal dihydroxy organosiloxane as soft segments, diisocyanate as hard segments and terminal dihydroxy compound containing disulfide bonds as a cross-linking agent, but the synthetic route is not limited to the synthetic route.
Fig. 2 is a synthetic route of a papermaking auxiliary agent using a terminal dihydroxy polyol and a terminal dihydroxy compound containing a disulfide bond as soft segments, diisocyanate as hard segments, and a terminal dihydroxy organosiloxane as a crosslinking agent, but is not limited thereto.
The terminal dihydroxy polyol is used as a soft segment of polyurethane, the terminal dihydroxy organosiloxane or the terminal dihydroxy monomer containing disulfide bonds can be used as a soft segment of polyurethane, the terminal dihydroxy monomer can also be used as a cross-linking agent of polyurethane, the diisocyanate is used as a hard segment of polyurethane, and the terminal hydroxy hyperbranched polyester is used as a core of polyurethane.
The application has the beneficial effects that:
the multifunctional paper-based material is prepared by introducing organic siloxane and disulfide bonds with thermoreversible dynamic exchange performance into a polyurethane auxiliary agent, and coating the polyurethane auxiliary agent on the surface of the paper-based material, the paper-based material not only has stronger waterproof performance based on the hydrophobic effect of the organic siloxane, but also can be self-bonded with the paper-based material only by utilizing the thermoreversible dynamic exchange effect of the disulfide bonds in the molecular structure of the polyurethane auxiliary agent and an interpenetrating network structure between paper-based fibers under the condition of not adding any adhesive when the paper-based material is bonded and hot-pressed for molding.
Drawings
FIG. 1 is a synthetic route 1 of a waterproof self-adhesive papermaking agent;
FIG. 2 is a synthetic route 2 for a waterproof self-adhesive papermaking agent;
FIG. 3 is a graph showing the contact angle between the paper-based material prepared in example 1-example 6 and the base paper;
FIG. 4 is the load-bearing capacity of a paper-based material under a 200g weight;
FIG. 5 shows the variation of the bonded paper-based material after 3 hours under the load-bearing action of a 200g weight (self-adhesive paper-based material according to the solution of the present application on the left side and commercially available glue-bonded paper-based material on the right side);
FIG. 6 is peel strength of paper;
FIG. 7 is a surface morphology block diagram; wherein a is base paper, b is paper coated by the polyurethane auxiliary agent of the embodiment-1, b 'is paper at a stripping position in the stripping process after the paper coated by the polyurethane auxiliary agent of the embodiment-1 is treated by a hot pressing process, c is paper coated by commercial glue, and c' is paper at the stripping position in the stripping process after the paper coated by the commercial glue is treated by the hot pressing process;
FIG. 8 is the rheological properties of the polyurethane coagent of examples 1-3;
fig. 9 is the rheological properties of the polyurethane coagent of examples 4-6.
Detailed Description
The method of preparing a water-repellent/self-adhesive papermaking aid according to the present application is further described below with reference to specific examples. The present application will be described in further detail with reference to specific examples, which are not intended to limit the scope of the application. Unless otherwise indicated, the reagents, apparatus and methods employed in the present application are those conventionally commercially available in the art and those conventionally used.
Example 1-example 3 terminal dihydroxy organosiloxane as the soft segment and a terminal dihydroxy compound containing disulfide bonds as the crosslinker.
Example 1:
the preparation method of the waterproof self-adhesive papermaking auxiliary agent comprises the following steps:
3.33g of polyethylene glycol (Mn=2000 g/mol) was dried in vacuo at 120℃for 2 hours, then mixed with 2.67g of terminal dihydroxy organosiloxane (Mn=800 g/mol), then placed in a three-necked flask, dissolved with 20mL of N, N-Dimethylformamide (DMF) under mechanical stirring of 200 r/min, and protected with nitrogen, 2.22g of isophorone diisocyanate was added dropwise to the above solution using a constant pressure dropping funnel, after mixing uniformly, 0.005g of dibutyltin dilaurate was added, the reaction temperature of the system was adjusted to 40℃and the polyurethane prepolymer having isocyanate groups at the terminal was obtained after 8 hours of reaction. After 0.5g of hyperbranched polyurethane (Mn=800 g/mol) with 8 hydroxyl groups at the end is dissolved in 10mLDMF, the mixture is slowly added into the reaction system and reacted for 6 hours at the temperature of 30 ℃ to obtain the hyperbranched polyurethane. After 0.60g of cystine is dissolved in 10mLDMF, the solution is slowly added into the reaction system and reacts for 6 hours at the temperature of 30 ℃ to obtain hyperbranched polyurethane solution.
In the above components, the molar ratio of the terminal dihydroxy polyol to the terminal dihydroxy organosiloxane was 0.5:1.
and pouring a part of the polyurethane solution into a polytetrafluoroethylene grinding tool to prepare a polyurethane film, and coating a part of the polyurethane film serving as an auxiliary agent on the surface of the paper-based material to prepare the multifunctional paper-based material.
Example 2:
the preparation method of the waterproof self-adhesive papermaking auxiliary agent comprises the following steps:
2.67g of polytetrahydrofuran (Mn=800 g/mol) was dried in vacuo at 120℃for 2 hours, then mixed with 8.33g of terminal dihydroxy organosiloxane (Mn=5000 g/mol), then placed in a three-necked flask, dissolved with 20mL of N, N-Dimethylformamide (DMF) under mechanical stirring of 200 r/min, and protected with nitrogen, 1.68g of hexamethylene diisocyanate was added dropwise to the above solution using a constant pressure dropping funnel, after mixing uniformly, 0.005g of dibutyltin dilaurate was added, the reaction temperature of the system was adjusted to 80℃and the polyurethane prepolymer having isocyanate groups at the terminal was obtained after 3 hours of reaction. After 0.83g of hyperbranched polyurethane (Mn=2000 g/mol) with 12 hydroxyl groups at the end was dissolved in 10mLDMF, the mixture was slowly added into the reaction system and reacted at 50℃for 6 hours to obtain the hyperbranched polyurethane. After 0.39g of bis (2-hydroxyethyl) disulfide was dissolved in 10ml of LDMF, the solution was slowly added to the above reaction system, and reacted at 50℃for 3 hours to obtain a hyperbranched polyurethane solution.
In the above components, the molar ratio of the terminal dihydroxy polyol to the terminal dihydroxy organosiloxane is 2:1.
and pouring a part of the polyurethane solution into a polytetrafluoroethylene grinding tool to prepare a polyurethane film, and coating a part of the polyurethane film serving as an auxiliary agent on the surface of the paper-based material to prepare the multifunctional paper-based material.
Example 3:
the preparation method of the waterproof self-adhesive papermaking auxiliary agent comprises the following steps:
5.0g of polytetrahydrofuran (Mn=2000 g/mol) was dried in vacuo at 120℃for 2 hours, then mixed with 5.0g of a terminal dihydroxy organosiloxane (Mn=2000 g/mol), then placed in a three-necked flask, dissolved with 20mL of N, N-Dimethylformamide (DMF) under mechanical stirring of 200 r/min, and protected with nitrogen, 2.50g of 4,4' -methylenebis (phenyl isocyanate) was added dropwise to the above solution using a constant pressure dropping funnel, after mixing uniformly, 0.005g of dibutyltin dilaurate was added, the reaction temperature of the system was adjusted to 60℃and the polyurethane prepolymer having isocyanate groups at the terminal was obtained after 4 hours of reaction. After 0.52g of hyperbranched polyurethane (Mn=5000 g/mol) with 48 hydroxyl groups at the end was dissolved in 10mLDMF, the mixture was slowly added into the reaction system and reacted at 40℃for 4 hours to obtain the hyperbranched polyurethane. After 0.62g of 2, 2-diaminodiphenyl disulfide is dissolved in 10 mM of LDMF, the mixture is slowly added into the reaction system and reacted for 4 hours at 40 ℃ to obtain hyperbranched polyurethane solution.
In the above components, the molar ratio of the terminal dihydroxy polyol to the terminal dihydroxy organosiloxane is 1:1.
and pouring a part of the polyurethane solution into a polytetrafluoroethylene grinding tool to prepare a polyurethane film, and coating a part of the polyurethane film serving as an auxiliary agent on the surface of the paper-based material to prepare the multifunctional paper-based material.
Examples 4 to 6, terminal dihydroxy compounds containing disulfide bonds were used as soft segments, and terminal dihydroxy organosiloxane was used as a crosslinking agent.
Example 4:
the preparation method of the waterproof self-adhesive papermaking auxiliary agent comprises the following steps:
3.33g of polyethylene glycol (Mn=2000 g/mol) was dried in vacuo at 120℃for 2 hours, then mixed with 0.80g of cystine, then placed in a three-necked flask, dissolved with 20mL of N, N-Dimethylformamide (DMF) under mechanical stirring of 200 r/min, and protected by nitrogen gas, 2.22g of isophorone diisocyanate was added dropwise to the above solution using a constant pressure dropping funnel, after uniform mixing, 0.005g of dibutyltin dilaurate was added, the reaction temperature of the system was adjusted to 40℃and the polyurethane prepolymer having isocyanate groups at the end was obtained after 8 hours of reaction. After 0.5g of hyperbranched polyurethane (Mn=800 g/mol) with 8 hydroxyl groups at the end is dissolved in 10mLDMF, the mixture is slowly added into the reaction system and reacted for 6 hours at the temperature of 30 ℃ to obtain the hyperbranched polyurethane. After 2.0g of terminal dihydroxy organosiloxane (Mn=800 g/mol) was dissolved in 10ml of LDMF, the mixture was slowly added to the above reaction system, and reacted at 30℃for 6 hours to obtain a hyperbranched polyurethane solution.
In the components, the mol ratio of the terminal dihydroxy polyol to the cystine is 0.5:1.
and pouring a part of the polyurethane solution into a polytetrafluoroethylene grinding tool to prepare a polyurethane film, and coating a part of the polyurethane film serving as an auxiliary agent on the surface of the paper-based material to prepare the multifunctional paper-based material.
Example 5:
the preparation method of the waterproof self-adhesive papermaking auxiliary agent comprises the following steps:
2.67g of polytetrahydrofuran (Mn=800 g/mol) was dried in vacuo at 120℃for 2 hours and then mixed with 0.26g of bis (2-hydroxyethyl) disulfide, then placed in a three-necked flask, and dissolved with 20mL of N, N-Dimethylformamide (DMF) under mechanical stirring of 200 r/min, and under nitrogen protection, 1.68g of hexamethylene diisocyanate was added dropwise to the above solution using a constant pressure dropping funnel, after mixing uniformly, 0.005g of dibutyltin dilaurate was added, the reaction temperature of the system was adjusted to 80℃and the polyurethane prepolymer having isocyanate groups at the end was obtained after 3 hours of reaction. After 0.83g of hyperbranched polyurethane (Mn=2000 g/mol) with 12 hydroxyl groups at the end was dissolved in 10mLDMF, the mixture was slowly added into the reaction system and reacted at 50℃for 6 hours to obtain the hyperbranched polyurethane. 12.5g of terminal dihydroxy organosiloxane (Mn=5000 g/mol) is dissolved in 10mLDMF, and then slowly added into the reaction system to react for 3 hours at 50 ℃ to obtain hyperbranched polyurethane solution.
In the above components, the molar ratio of the terminal dihydroxy polyol to the terminal dihydroxy organosiloxane is 2:1.
and pouring a part of the polyurethane solution into a polytetrafluoroethylene grinding tool to prepare a polyurethane film, and coating a part of the polyurethane film serving as an auxiliary agent on the surface of the paper-based material to prepare the multifunctional paper-based material.
Example 6:
the preparation method of the waterproof self-adhesive papermaking auxiliary agent comprises the following steps:
5.0g of polytetrahydrofuran (Mn=2000 g/mol) was dried in vacuo at 120℃for 2 hours, then mixed with 0.62g of 2, 2-diaminodiphenyl disulfide, then placed in a three-necked flask, dissolved with 20ml of N, N-Dimethylformamide (DMF) under mechanical stirring of 200 r/min, purged with nitrogen, 2.50g of 4,4' -methylenebis (phenyl isocyanate) were added dropwise to the above solution using a constant pressure dropping funnel, after mixing uniformly, 0.005g of dibutyltin dilaurate was added, the reaction temperature of the system was adjusted to 60℃and the polyurethane prepolymer having isocyanate groups at the end was obtained after 4 hours of reaction. After 0.52g of hyperbranched polyurethane (Mn=5000 g/mol) with 48 hydroxyl groups at the end was dissolved in 10mLDMF, the mixture was slowly added into the reaction system and reacted at 40℃for 4 hours to obtain the hyperbranched polyurethane. After 5.0g of terminal dihydroxy organosiloxane (Mn=2000 g/mol) was dissolved in 10ml of LDMF, the mixture was slowly added to the above reaction system, and reacted at 40℃for 4 hours to obtain a hyperbranched polyurethane solution.
In the above components, the molar ratio of the terminal dihydroxy polyol to the terminal dihydroxy organosiloxane is 1:1.
and pouring a part of the polyurethane solution into a polytetrafluoroethylene grinding tool to prepare a polyurethane film, and coating a part of the polyurethane film serving as an auxiliary agent on the surface of the paper-based material to prepare the multifunctional paper-based material.
Examples of the effects
1. The contact angle test is carried out on the base paper and the multifunctional paper-based material prepared by the scheme of the embodiment, the experimental result is shown in fig. 3, and as can be seen from fig. 3, the polyurethane papermaking auxiliary agent prepared by the scheme of the application can obviously improve the waterproof performance of the paper-based material.
2. The self-adhesive properties of the paper-based material were determined by peel strength.
Firstly, concentrating the concentration of the polyurethane auxiliary agent to 50% by adopting a rotary evaporator, uniformly coating the polyurethane auxiliary agent on the surface of paper by using a coating rod, airing at normal temperature to obtain a multifunctional paper-based material, spreading the paper above base paper with the same size, and then simultaneously placing two papers into a hot press, wherein the temperature of the hot press is controlled to be 100 ℃, the pressure is 1000kg, and the time is 10min. The load-bearing capacity of the bonded paper-based material was measured by using a 200g weight, the peel strength of the paper was measured by using a universal tensile machine, and the test results are shown in fig. 4, 5 and 6:
it can be observed from fig. 4 that the load-bearing capacity of the bonded paper-based material can reach 200g (weight of weight). In addition, the same test was performed on the paper-based material by using the commercial glue, and it was found through fig. 5 (the left side is the self-adhesive paper-based material of the present application, and the right side is the paper-based material adhered by the commercial glue), after 3 hours under the load-bearing effect of the 200g weight, the self-adhesive paper-based material prepared by the present application still maintains a good adhesion performance, and the paper-based material adhered by the commercial glue has a significant tearing phenomenon.
As shown in fig. 6, after the polyurethane auxiliary agent prepared in example 1-example 6 is coated on the paper material, the self-bonding is carried out on the paper, and the bonded paper-based material has higher peel strength, which indicates that the polyurethane papermaking auxiliary agent prepared by the experimental scheme of the application can endow the paper-based material with higher self-bonding performance.
3. In order to further demonstrate the change in the release process of the bonded paper-based material, the applicant of the present application observed the morphological changes of the paper-based surface before and after tearing using a scanning electron microscope, taking the polyurethane auxiliary agent prepared in example-1 as an example.
Fig. 7a shows the surface morphology of the uncoated base paper, and it can be seen that there are distinct filaments, fig. 7b and 7b 'show the morphology of the paper coated with the polyurethane auxiliary agent of example-1 and the surface morphology of the paper after stripping, respectively, and it can be seen from fig. 7b and 7b' that the surface fiber structure of the paper coated with the polyurethane auxiliary agent is covered, after the hot pressing process, the bonded paper base material is torn off, the surface of the paper shows distinct cellulose filament structure again, and there are distinct fiber burrs on the surface of the fibers compared with the base paper, which means that the structure of the cellulose itself is destroyed during stripping, instead of the adhesion of the auxiliary agent itself being weak. In contrast, the paper coated with the commercially available glue, after the same peel strength test, showed a significant fiber at the peel interface, but the glue was still present on the fiber surface (fig. 7c and 7 c'), which demonstrates that the polyurethane adjuvant prepared by the experimental scheme of the present application has a strong self-adhesive function on the paper-based material.
4. In order to analyze the self-adhesion mechanism of the auxiliary agent to paper, a high-efficiency rotary rheometer is adopted to measure the dynamic rheological property of the polyurethane auxiliary agent film
As can be seen from fig. 8 and 9, the polyurethane auxiliary agent prepared in examples 1 to 6 has a storage modulus G' (solid) and a loss modulus g″ (hollow) which are both intersected at a low frequency of 60 ℃, which means that the polyurethane can reach a viscous state at a temperature higher than 60 ℃, and the molecular chains themselves have a strong dynamic exchange capability, and when the polyurethane auxiliary agent is coated on the paper-based surface, molecular chain entanglement is formed between the polyurethane molecular chains and the paper-based fibers at the hot pressing temperature of the hot press, and dynamic exchange occurs through disulfide bonds in the polyurethane molecular chains, so that an interpenetrating network is formed between the polyurethane and the cellulose, thereby generating self-bonding effect.
Claims (10)
1. The waterproof self-adhesive papermaking auxiliary agent is characterized by comprising the following raw materials in parts by weight: a terminal dihydroxy polyol, a terminal dihydroxy organosiloxane, a terminal dihydroxy monomer containing disulfide bonds, a diisocyanate, a terminal hydroxy hyperbranched polyester;
the molar ratio of total hydroxyl groups (-OH) in the terminal dihydroxy polyol, the terminal dihydroxy organosiloxane and the disulfide bond-containing terminal dihydroxy compound to isocyanate groups (-NCO) in the diisocyanate is n (-OH): n (-NCO) =3: 4, the molar ratio of hydroxyl (-OH) in the hydroxyl-terminated hyperbranched polyester to isocyanate (-NCO) in the diisocyanate is n (-OH): n (-NCO) =1: 4.
2. the water-repellent self-adhesive papermaking auxiliary according to claim 1, wherein when a terminal dihydroxy polyol and a terminal dihydroxy organosiloxane are used as the soft segments and a terminal dihydroxy monomer containing disulfide bonds is used as the crosslinking agent, the molar ratio of the terminal dihydroxy polyol to the terminal dihydroxy organosiloxane is 0.5: 1-2: 1, the molar ratio of the whole of the terminal dihydroxy polyol and the terminal dihydroxy organosiloxane to the diisocyanato is 1:2, the mol ratio of the terminal dihydroxy monomer containing disulfide bond to the diisocyanato is 1:4.
3. the water-repellent self-adhesive papermaking auxiliary according to claim 1, wherein when a terminal dihydroxy polyol and a terminal dihydroxy monomer containing disulfide bonds are used as the soft segment and a terminal dihydroxy organosiloxane is used as the crosslinking agent, the molar ratio of the terminal dihydroxy polyol to the terminal dihydroxy organosiloxane is 0.5: 1-2: 1, the molar ratio of the whole of the terminal dihydroxy polyol and the terminal dihydroxy organosiloxane to the diisocyanato is 1:2, the molar ratio of terminal dihydroxy organosiloxane to diisocyanato is 1:4.
4. the waterproof self-adhesive papermaking auxiliary agent according to claim 1, wherein the polyalcohol is one or two of polyethylene glycol and polytetrahydrofuran, and the molecular weight of the polyalcohol is 800-5000 g/mol; and/or the diisocyanate is one or more of isophorone diisocyanate, hexamethylene diisocyanate, 4' -methylenebis (phenyl isocyanate); and/or the molecular weight of the terminal dihydroxy organosiloxane is 800-5000 g/mol; and/or the terminal dihydroxy monomer containing disulfide bond is one or more of cystine, bis (2-hydroxyethyl) disulfide and 2, 2-diaminodiphenyl disulfide; and/or the hydroxyl number of the terminal hydroxyl-terminated hyperbranched polyester can be 8, 12, 24, 36 and 48, and the corresponding molecular weight is 800-5000 g/mol.
5. A method of preparing the waterproof self-adhesive papermaking auxiliary according to claim 1, comprising the steps of:
s1, performing condensation reaction on terminal dihydroxy polyol, terminal dihydroxy organosiloxane and diisocyanate under the action of a catalyst dibutyl tin dilaurate to synthesize an isocyanate-terminated polyurethane prepolymer;
s2, adding hydroxyl-terminated hyperbranched polyester into a reaction system S1, and preparing hyperbranched polyurethane through condensation reaction of hydroxyl in the molecular structure of the hydroxyl-terminated hyperbranched polyester and isocyanate residual in the S1;
s3, adding a terminal dihydroxy monomer containing disulfide bonds into the S2 reaction system, and crosslinking different hyperbranched polyurethanes together by utilizing the reaction between hydroxyl groups at two ends of the compound and residual isocyanate groups in the polymerization reaction to synthesize the polyurethane auxiliary agent with higher crosslinking degree.
6. The method according to claim 5, wherein the terminal dihydroxy organosiloxane of step S1 is interchanged with the disulfide bond-containing terminal dihydroxy monomer of step S3.
7. The process according to claim 5, wherein the reaction temperature in the step S1 is 40 to 80℃and the reaction time is 3 to 8 hours.
8. The preparation method according to claim 5, wherein the reaction temperature in the step S2 is 30-50 ℃ and the reaction time is 3-6 h; and/or the reaction temperature in the step S3 is 30-50 ℃ and the reaction time is 3-6 h.
9. Use of the waterproof self-adhesive papermaking aid of claim 1 or prepared by the method of claim 5 as a waterproof layer for paper.
10. The use according to claim 9, characterized in that the obtained auxiliary agent is applied to a paper-based material and hot pressed.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202310803900.9A CN116732816A (en) | 2023-07-03 | 2023-07-03 | Waterproof self-adhesive papermaking auxiliary agent and preparation method and application thereof |
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| CN202310803900.9A CN116732816A (en) | 2023-07-03 | 2023-07-03 | Waterproof self-adhesive papermaking auxiliary agent and preparation method and application thereof |
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