CN114687240A - Preparation method of modified polyurethane/AKD sizing agent - Google Patents
Preparation method of modified polyurethane/AKD sizing agent Download PDFInfo
- Publication number
- CN114687240A CN114687240A CN202210297931.7A CN202210297931A CN114687240A CN 114687240 A CN114687240 A CN 114687240A CN 202210297931 A CN202210297931 A CN 202210297931A CN 114687240 A CN114687240 A CN 114687240A
- Authority
- CN
- China
- Prior art keywords
- sizing agent
- reaction
- akd
- modified polyurethane
- shearing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004513 sizing Methods 0.000 title claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 20
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 14
- 239000004814 polyurethane Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000010008 shearing Methods 0.000 claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 229960000583 acetic acid Drugs 0.000 claims abstract description 10
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 10
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000002009 diols Chemical class 0.000 claims abstract description 9
- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 9
- 239000004632 polycaprolactone Substances 0.000 claims abstract description 9
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 8
- 235000019864 coconut oil Nutrition 0.000 claims abstract description 8
- 239000003240 coconut oil Substances 0.000 claims abstract description 8
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 8
- 229930195729 fatty acid Natural products 0.000 claims abstract description 8
- 239000000194 fatty acid Substances 0.000 claims abstract description 8
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 238000007599 discharging Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims 2
- 239000000126 substance Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 1
- 239000002904 solvent Substances 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
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/17—Ketenes, e.g. ketene dimers
-
- 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
- D21H17/54—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 nitrogen
- D21H17/57—Polyureas; Polyurethanes
-
- 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
- D21H17/72—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic material
Abstract
The invention belongs to the technical field of papermaking chemistry, and discloses a preparation method of a modified polyurethane/AKD sizing agent, which comprises the following steps: 1) mixing 2, 4-toluene diisocyanate, AKD and polycaprolactone diol according to a certain proportion, heating to 160 ℃ and introducing nitrogen for reaction for 2 hours; 2) after the reaction is finished, cooling to 85 ℃, adding glacial acetic acid, stirring for 10 minutes, and then adding coconut oil fatty acid to react for 4 hours; 3) adding a certain amount of hot water into the reaction product under high-speed shearing, shearing at high speed for half an hour, cooling and discharging. The sizing agent obtained by the invention has the advantages of improved strength, high water resistance, degradability and the like.
Description
Technical Field
The invention belongs to the technical field of papermaking chemistry, and particularly relates to a preparation method of a modified polyurethane/AKD sizing agent.
Background
The invention relates to a paper making wet end additive chemical. In recent years, paper has been used as a substitute for plastic, and the amount of paper used has been increasing year by year, so that paper having high water resistance and high barrier properties has become the mainstream in the field of packaging. This places even greater demands on paper making chemicals, especially sizing chemicals. Papermaking chemicals are required not only to improve paper properties such as water resistance, oil resistance, wet strength, oxygen barrier, smoothness, printability, softness, etc., but also to be green and degradable. AKD, which is the most representative chemical for neutral sizing, mainly provides water resistance, but is inferior in oxygen barrier property, paper strength improvement, etc., and is also not satisfactory in water resistance for a long time. The polyurethane modified AKD sizing agent prepared by the method has degradability, has the advantages of polyurethane and AKD, and can endow paper with good oxygen resistance and water resistance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of a modified polyurethane/AKD sizing agent.
In order to realize the aim, the invention provides a preparation method of a modified polyurethane/AKD sizing agent, which comprises the following steps:
1) mixing 2, 4-toluene diisocyanate, AKD and polycaprolactone diol according to a certain proportion, heating to 160 ℃, and introducing nitrogen for reaction for 2 hours; after the reaction is finished, obtaining a reaction system;
2) cooling the reaction system obtained in the step 1) to 85 ℃, adding glacial acetic acid, stirring, and adding coconut oil fatty acid to react for 4 hours; obtaining a mixed reaction product;
3) adding a certain amount of hot water into the mixed reaction product obtained in the step 2) under high-speed shearing, shearing at a high speed for half an hour under a certain rotating speed, and discharging after cooling to obtain the sizing agent.
Further, in the step 1), the mass ratio of the 2, 4-toluene diisocyanate, AKD and polycaprolactone diol is 5: 80-120: 10-20.
Further, in the step 2), the adding amount of the glacial acetic acid is 10-30% of the mass of the reaction system, and the stirring time is 10min after the glacial acetic acid is added; the addition amount of the coconut oil fatty acid is 20-50% of the mass of the reaction system.
Further, in the step 3), the temperature of the added hot water is 80-100 ℃, and the adding amount of the hot water accounts for 70-80% of the mass of the whole sizing agent.
Further, in the step 3), the high speed shearing speed is 10000-.
The invention has the beneficial effects that:
the sizing agent obtained by the invention has the advantages of simple preparation method and good water-resistant effect, and can be used for the aspects of high water resistance, oxygen resistance and the like of packaging materials.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments. It is to be understood that the specific embodiments described herein are for purposes of illustration only and are not to be construed as limitations of the invention.
In addition, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict. The present disclosure will be described in detail with reference to embodiments.
Example 1
Putting 5g of 2, 4-toluene diisocyanate, 80g of AKD and 10g of polycaprolactone diol into a four-neck flask, heating to 120 ℃, and introducing nitrogen to react for 2 hours; after the reaction is finished, cooling to 85 ℃, adding 9.5g of glacial acetic acid, stirring for 10 minutes, and then adding 19g of coconut oil fatty acid to react for 4 hours; shearing the reaction product at a high speed at 10000r/min, adding 494g of hot water of 80 ℃, shearing at a high speed for half an hour, cooling and discharging.
Example 2
Putting 5g of 2, 4-toluene diisocyanate, 100g of AKD and 15g of polycaprolactone diol into a four-neck flask, heating to 120 ℃, and introducing nitrogen to react for 2 hours; after the reaction is finished, cooling to 85 ℃, adding 24g of glacial acetic acid, stirring for 10 minutes, and then adding 36g of coconut oil fatty acid to react for 4 hours; shearing the reaction product at high speed at 12000r/min, adding a certain amount of 420g of 90 ℃ hot water, shearing at high speed for half an hour, cooling and discharging.
Example 3
Putting 5g of 2, 4-toluene diisocyanate, 120g of AKD and 20g of polycaprolactone diol into a four-neck flask, heating to 150 ℃, and introducing nitrogen to react for 2 hours; after the reaction is finished, cooling to 85 ℃, adding 43.5g of glacial acetic acid, stirring for 10 minutes, and then adding 72.5g of coconut oil fatty acid to react for 4 hours; shearing the reaction product at high speed at the rotating speed of 15000r/min, adding a certain amount of 1000g of hot water with the temperature of 100 ℃, shearing at high speed for half an hour, cooling and discharging.
Comparative example 1
Melting 120g of AKD to 85 ℃, adding 50g of a polymeric emulsifier (poly diallyl dimethyl ammonium chloride with solid content of 40%), heating to 870g of water to 100 ℃, starting high shear, slowly adding hot water into the AKD, shearing for 30 minutes at the speed of 10000r/min, and cooling for later use.
Comparative example 2
10-20g of polycaprolactone diol and 10g of 2, 4-Toluene Diisocyanate (TDI), stirring and introducing nitrogen, reacting for 3h at 80 ℃, adding a small amount of acetone solvent, stirring for 10min, then adding a catalyst, dimethylolpropionic acid (DMPA) and a cross-linking agent Trimethylolpropane (TMP), reacting for 4h, then adding triethylamine into the polyurethane prepolymer under rapid stirring for 5min, then adding calculated water for emulsification, and after 10min, removing acetone under reduced pressure to obtain an emulsion with the solid content of 30%.
The test mode is as follows: the sizing agent is coated on the surface of paper according to the quantitative ratio of 6-10g/m2d, and the water resistance performance is measured.
It will be understood by those skilled in the art that the foregoing embodiments are merely for clarity of illustration of the disclosure and are not intended to limit the scope of the disclosure. Other variations or modifications may occur to those skilled in the art, based on the foregoing disclosure, and are still within the scope of the present disclosure.
Claims (7)
1. A preparation method of a modified polyurethane/AKD sizing agent is characterized by comprising the following steps:
1) mixing 2, 4-toluene diisocyanate, AKD and polycaprolactone diol according to a certain proportion, heating to a certain temperature, and introducing nitrogen for reaction; after the reaction is finished, obtaining a reaction system;
2) cooling the reaction system obtained in the step 1) to a certain temperature, adding glacial acetic acid, stirring, and adding coconut oil fatty acid for reaction; obtaining a mixed reaction product;
3) adding a certain amount of hot water into the mixed reaction product obtained in the step 2) under high-speed shearing, shearing at a high speed under a certain rotating speed, cooling, and discharging to obtain the sizing agent.
2. The method for preparing a modified polyurethane/AKD sizing agent according to claim 1, wherein in step 1), the mass ratio of 2, 4-toluene diisocyanate, AKD and polycaprolactone diol is 5: 80-120: 10-20, the reaction temperature is 120-160 ℃, and the reaction time is 2 hours.
3. The method for preparing a modified polyurethane/AKD sizing agent according to claim 1, wherein in the step 2), the temperature of the reaction system obtained in the step 1) is reduced to 85 ℃.
4. The method for preparing a modified polyurethane/AKD sizing agent according to claim 1, wherein in the step 2), the amount of the glacial acetic acid added is 10-30% of the mass of the reaction system, and the stirring time after adding the glacial acetic acid is 10 min; the addition amount of the coconut oil fatty acid is 20-50% of the mass of the reaction system.
5. The method for preparing a modified polyurethane/AKD sizing agent according to claim 1, wherein in step 2), the reaction time is 4 hours.
6. The method for preparing a modified polyurethane/AKD sizing agent according to claim 1, wherein in step 3), the temperature of the hot water is 80-100 ℃, and the amount of the hot water added is 70-80% of the total weight of the sizing agent.
7. The method as set forth in claim 1, wherein the high speed shearing speed in step 3) is 10000-15000r/min for half an hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210297931.7A CN114687240A (en) | 2022-03-24 | 2022-03-24 | Preparation method of modified polyurethane/AKD sizing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210297931.7A CN114687240A (en) | 2022-03-24 | 2022-03-24 | Preparation method of modified polyurethane/AKD sizing agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114687240A true CN114687240A (en) | 2022-07-01 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210297931.7A Pending CN114687240A (en) | 2022-03-24 | 2022-03-24 | Preparation method of modified polyurethane/AKD sizing agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114687240A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103739788A (en) * | 2013-12-20 | 2014-04-23 | 天津商业大学 | Preparation method of surface sizing agent |
| CN113265901A (en) * | 2021-05-13 | 2021-08-17 | 南京林业大学 | Dimer acid-based waterborne polyurethane surface sizing agent and preparation method and application thereof |
-
2022
- 2022-03-24 CN CN202210297931.7A patent/CN114687240A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103739788A (en) * | 2013-12-20 | 2014-04-23 | 天津商业大学 | Preparation method of surface sizing agent |
| CN113265901A (en) * | 2021-05-13 | 2021-08-17 | 南京林业大学 | Dimer acid-based waterborne polyurethane surface sizing agent and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 刘瑞雪, 河南大学出版社 * |
| 袁剑辉: "AKD改性聚氨酯预聚体共混物的制备及其", 《造纸化学品》 * |
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|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220701 |
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| RJ01 | Rejection of invention patent application after publication |