CN115058919A - Preparation method of rosin substitute/cationic rosin sizing agent - Google Patents
Preparation method of rosin substitute/cationic rosin sizing agent Download PDFInfo
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- CN115058919A CN115058919A CN202210756986.XA CN202210756986A CN115058919A CN 115058919 A CN115058919 A CN 115058919A CN 202210756986 A CN202210756986 A CN 202210756986A CN 115058919 A CN115058919 A CN 115058919A
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- Prior art keywords
- rosin
- cationic
- sizing agent
- petroleum resin
- substitute
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- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 title claims abstract description 77
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 title claims abstract description 77
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 238000004513 sizing Methods 0.000 title claims abstract description 42
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000003208 petroleum Substances 0.000 claims abstract description 41
- 239000011347 resin Substances 0.000 claims abstract description 40
- 229920005989 resin Polymers 0.000 claims abstract description 40
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000000839 emulsion Substances 0.000 claims abstract description 21
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 12
- 238000012986 modification Methods 0.000 claims abstract description 12
- 230000004048 modification Effects 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000005120 petroleum cracking Methods 0.000 claims abstract description 11
- 239000012188 paraffin wax Substances 0.000 claims abstract description 8
- 238000009775 high-speed stirring Methods 0.000 claims abstract description 7
- 239000011951 cationic catalyst Substances 0.000 claims abstract description 6
- 229920006317 cationic polymer Polymers 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- 238000001816 cooling Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 6
- 229920002647 polyamide Polymers 0.000 claims description 6
- 229920000768 polyamine Polymers 0.000 claims description 6
- 238000000265 homogenisation Methods 0.000 claims 1
- 239000006260 foam Substances 0.000 abstract description 14
- 230000005764 inhibitory process Effects 0.000 abstract description 6
- 239000002518 antifoaming agent Substances 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 239000007787 solid Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000005587 bubbling Effects 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 208000023445 Congenital pulmonary airway malformation Diseases 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000004383 yellowing 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
-
- 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
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
-
- 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
- D21H17/60—Waxes
-
- 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
- D21H17/62—Rosin; Derivatives thereof
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Paper (AREA)
Abstract
The invention provides a preparation method of a rosin substitute/cationic rosin sizing agent, which comprises the following steps: polymerizing petroleum cracking fractions under the action of an effective amount of cationic catalyst, adding maleic anhydride for grafting modification after the reaction is finished, and adding paraffin after the temperature is reduced to obtain modified petroleum resin; mixing rosin and modified petroleum resin according to the proportion of (70-95): (5-30), heating until the rosin and the modified petroleum resin are completely melted, adding the cationic polymer emulsifier under high-speed stirring to obtain a metastable emulsion, and homogenizing the metastable emulsion under high pressure to obtain the rosin substitute/cationic rosin sizing agent. According to the invention, the C5 and C9 fractions are subjected to catalytic polymerization and then added with maleic anhydride for graft modification, so that the defect that petroleum resin is easy to foam can be overcome, the prepared rosin substitute/cationic rosin sizing agent has excellent foam inhibition performance, no additional defoaming agent is required, and the economic benefit of the pulp sizing agent can be improved.
Description
Technical Field
The invention relates to the technical field of rosin sizing agent preparation, in particular to a preparation method of a rosin substitute/cationic rosin sizing agent.
Background
At present, various rosin sizing agents are mainly used as domestic sizing agents, but due to the fact that the price of rosin raw materials fluctuates, the sizing cost is difficult to control, and rosin sizing agents are mostly used for sizing under the acidic condition, so that the rosin sizing agent has high corrosion to equipment and easy yellowing of paper, and therefore a rosin substitute which is low in cost and easy to manufacture needs to be developed as a novel sizing agent.
On the other hand, with the increasing demand for petroleum throughout the world, especially china, the production of C5, C9 fractions as ethylene cracking by-products is increasing accordingly. The field of papermaking chemicals, which is becoming more and more prominent, is also at a stage of changing from specialized to comprehensive production, from large-volume production, small-volume production, and large-volume production.
Chinese patent CN102995488A discloses a preparation method of a cationic rosin/C9 petroleum resin sizing agent, which takes vinyl monomers such as styrene, acrylate monomers, acrylamide, cationic monomers and the like as comonomers under the action of an organic solvent which can be mutually dissolved with water, and prepares a cationic styrene-acrylic polymer through solution polymerization; the cationic rosin/C9 petroleum resin emulsion with good stability and sizing performance is prepared by taking the cationic polymer as a cationic polymer surfactant and emulsifying and dispersing a mixture of rosin and C9 petroleum resin. However, the cationic rosin/C9 petroleum resin emulsion still has the defect of easy foaming due to the characteristics of the C5 and C9 petroleum resin emulsions, and an additional defoaming agent is required to be added for foam inhibition.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of a rosin substitute/cationic rosin sizing agent with excellent foam inhibition performance, and no additional foam inhibitor is needed to be added, so that the technical problems in the prior art are solved.
The invention is realized by adopting the following technical scheme:
a preparation method of a rosin substitute/cationic rosin sizing agent comprises the following steps:
s1, polymerizing the petroleum cracking fraction at 50-70 ℃ under the action of an effective amount of cationic catalyst for 1-5h, adding maleic anhydride for graft modification at 210 ℃ at 170-6 h after the reaction is finished; cooling to 130 ℃ and 160 ℃, adding paraffin for 0.5-1h, and cooling to room temperature to obtain modified petroleum resin;
s2, mixing rosin and the modified petroleum resin according to the weight ratio of (70-95): (5-30), heating to 150 ℃, after the rosin and the modified petroleum resin are completely melted, adding a 90-95 ℃ cationic polymer emulsifier under high-speed stirring to obtain a metastable emulsion, homogenizing the metastable emulsion under high pressure, cooling and obtaining the rosin substitute/cationic rosin sizing agent.
The petroleum cracking fraction refers to C5 and/or C9 fractions.
The inventor unexpectedly finds that the defect that C5 and C9 petroleum resins are easy to foam can be overcome by adding maleic anhydride for graft modification after catalytic polymerization of C5 and C9 fractions, and the rosin substitute/cationic rosin sizing agent prepared by replacing a part of rosin with the modified petroleum resin has excellent foam inhibition performance without adding an additional defoaming agent. The present invention has been completed based on the above findings.
The inventor further researches and discovers that the addition amount of the maleic anhydride in the step S1 is too low, namely the grafting amount is small, and the effective foam inhibiting and defoaming effect cannot be achieved; and too high a maleic anhydride addition, i.e., too much grafting, results in poor sizing of the product. The preferred amount of maleic anhydride added is 5 to 20 parts, more preferably 5 to 10 parts, per 100 parts by weight of the petroleum cracking fraction, taking into consideration the sizing properties and the foam suppressing effect of the product itself.
Preferably, in step S1, the weight amounts of the components are as follows: 100 parts of petroleum cracking fraction, 5-10 parts of maleic anhydride and 4-10 parts of paraffin.
The cationic catalyst in step S1 is selected from AlCl 3 、BF 3 、SnCl 4 、ZnCl 2 、TiCl 4 Preferably in an amount of 0.4 to 1 wt% based on the petroleum cracking fraction.
The cationic polymeric emulsifier in step S2 can be an emulsifier commonly used in the art, such as a cationic styrene-acrylic polymer disclosed in CN 102995488A. For better foam inhibition, polyamide polyamine epichlorohydrin is preferred. The amount thereof is preferably 6 to 16% by weight based on the total weight of the rosin and the modified petroleum resin.
Preferably, the high-pressure homogenizing pressure in the step S2 is 20-30 MPa.
Compared with the prior art, the invention has the beneficial effects that: according to the invention, the C5 and C9 fractions are subjected to catalytic polymerization and then added with maleic anhydride for graft modification, so that the defect that C5 and C9 petroleum resins are easy to foam can be overcome, the modified petroleum resins are used for replacing a part of rosin, and the prepared rosin substitute/cationic rosin sizing agent has excellent foam inhibition performance, and the additional addition of a defoaming agent is not needed, so that the economic benefit of the pulp sizing agent can be improved.
Detailed Description
The following description is presented to disclose the invention so as to enable any person skilled in the art to practice the invention. The preferred embodiments described below are intended to be illustrative only and are not intended to be limiting as other obvious modifications may occur to those skilled in the art. The basic principles of the invention, as defined in the following description, may be applied to other embodiments, variations, modifications, equivalents, and other technical solutions without departing from the spirit and scope of the invention.
The apparatus or raw materials in the present invention are not indicated by manufacturers, and are all conventional commercial apparatuses or raw materials.
If not mentioned, the detection indexes related in the embodiment of the invention are all detected by adopting the conventional detection method in the field.
Example 1
1) Preparation of rosin substitute:
500g of C5 fraction and 5g of AlCl were weighed out 3 Putting into a dry reaction kettle, setting the temperature at 70 ℃, reacting for 1h, adjusting the temperature to 210 ℃ after the reaction is finished, adding 50g of maleic anhydride for grafting modification,the reaction time is 3 h; after the reaction is finished, the temperature is reduced to 160 ℃, 50g of paraffin is added, the reaction is carried out for 1h, and the stirring speed is controlled at 400rpm in the whole reaction process. Stopping stirring after the reaction is finished, and cooling to room temperature to obtain modified C5 petroleum resin;
2) preparation of cationic rosin and rosin substitute sizing agent:
taking 200g of emulsifier polyamide polyamine epichlorohydrin with solid content of 6-7%, heating to about 95 ℃ for standby.
Adding 70g of rosin and 30g of modified petroleum resin into a reaction kettle, heating to 120 ℃, adding an emulsifier under high-speed stirring after the rosin and the modified petroleum resin are completely melted to obtain a metastable emulsion, homogenizing the metastable emulsion under the high pressure of 30MPa, cooling, and adjusting the solid content to 30-40% to obtain the rosin substitute/cationic rosin sizing agent emulsion.
Example 2
1) Preparation of rosin substitute:
500g of C9 fraction and 2g of BF were weighed out 3 Putting the mixture into a dry reaction kettle, setting the temperature to be 50 ℃, reacting for 5 hours, adjusting the temperature to 170 ℃ after the reaction is finished, and adding 25g of maleic anhydride for grafting modification, wherein the reaction time is 6 hours; after the reaction is finished, the temperature is reduced to 130 ℃, 25g of paraffin is added, the reaction is carried out for 0.5h, and the stirring speed is controlled at 200rpm in the whole reaction process. Stopping stirring after the reaction is finished, and cooling to room temperature to obtain modified C9 petroleum resin;
2) preparation of cationic rosin and rosin substitute sizing agent:
taking 75g of emulsifier polyamide polyamine epichlorohydrin with the solid content of 16-17%, and heating to about 90 ℃ for later use.
Adding 95g of rosin and 5g of modified petroleum resin into a reaction kettle, heating to 150 ℃, adding an emulsifier under high-speed stirring after the rosin and the modified petroleum resin are completely melted to obtain a metastable emulsion, homogenizing the metastable emulsion under the high pressure of 25MPa, cooling, and adjusting the solid content to 30-40% to obtain the rosin substitute/cationic rosin sizing agent emulsion.
Example 3
1) Preparation of rosin substitute:
a mixture of 500g of C5, C9 fraction and 3g of TiCl were weighed out 4 Putting the mixture into a dry reaction kettle, setting the temperature to be 60 ℃, reacting for 3 hours, adding the mixture after the reaction is finished, adjusting the temperature to be 200 ℃, and adding 30g of maleic anhydride for grafting modification, wherein the reaction time is 4 hours; after the reaction is finished, the temperature is reduced to 150 ℃, 20g of paraffin is added, the reaction is carried out for 0.5h, and the stirring speed is controlled at 300rpm in the whole reaction process. Stopping stirring after the reaction is finished, and cooling to room temperature to obtain modified C5 and C9 copolymerized petroleum resin;
2) preparation of cationic rosin and rosin substitute sizing agent:
taking 75g of polyamide polyamine epichlorohydrin with the solid content of 16-17%, and heating to about 90 ℃ for later use.
Adding 80g of rosin and 20g of modified petroleum resin into a reaction kettle, heating to 150 ℃, adding an emulsifier under high-speed stirring after the rosin and the modified petroleum resin are completely melted to obtain a metastable emulsion, homogenizing the metastable emulsion under the high pressure of 20MPa, cooling, and adjusting the solid content to 30-40% to obtain the rosin substitute/cationic rosin sizing agent emulsion.
Comparative example
1) Preparation of C5 Petroleum resin:
500g of C5 fraction and 5g of AlCl were weighed out 3 Putting into a dry reaction kettle, setting the temperature at 70 ℃, reacting for 1h, and cooling to room temperature after the reaction is finished to obtain C5 petroleum resin;
2) preparation of cationic rosin and C5 petroleum resin sizing agent:
taking 200g of polyamide polyamine epichlorohydrin with solid content of 6-7%, heating to about 95 ℃ for standby.
Adding 70g of rosin and 30g of C5 petroleum resin into a reaction kettle, heating to 120 ℃, adding an emulsifier under high-speed stirring after the rosin and the petroleum resin are completely melted to obtain a metastable emulsion, homogenizing the metastable emulsion under the high pressure of 30MPa, cooling, and adjusting the solid content to 30-40% to obtain the C5 petroleum resin/cationic rosin sizing agent emulsion.
Application example 1
The examples and comparative examples were run for handsheet addition comparative applications. The specific experimental process is as follows:
papermaking quantitative of 100g/m 2 (ii) a Slurry (85%) + rosin size 18kg/t + talcum powder 15% + CPAM (100ppm) + microparticle 200 ppm; weighing the slurry according to the process, sequentially adding rosin size, talcum powder and CPAM, stirring for 1min respectively, uniformly mixing, taking down the prepared slurry, using a semi-automatic paper sheet former to make sheets, using a standard paper sheet squeezer to squeeze the sheets, drying the sheets by a glazing machine, and detecting the 1minCobb value of the paper sample.
The test results are shown in table 1:
TABLE 1 comparison of Water resistance after sizing for different samples
From the water absorption value of a handsheet sample, the petroleum resin replaces part of the rosin to prepare the sizing agent, and the water-resistant effect of the sizing agent is better than that of the petroleum resin/cationic rosin sizing agent which is not grafted and modified. After grafting, the petroleum resin is introduced with active groups, so that the petroleum resin is more favorable for being combined with fibers, and the hydrophobic nonpolar part is turned to the outer side of the fibers, thereby reducing the surface tension of paper and improving the lyophobic property of the paper.
Application example 2
Each example and comparative example were subjected to a foaming defoaming verification experiment, verification method: placing 5L of white water in a 25L container, adding 75g of the sizing agent samples prepared in examples 1-3 and comparative examples, stirring uniformly, carrying out bubbling for 30min by using a bubbling machine, measuring the foam height after bubbling, and measuring the foam height after defoaming after standing for 5 min. The test results are shown in table 2:
| sample (I) | Bubbling deviceRear height/cm | Height/cm after defoaming |
| Example 1 | 11 | 0 |
| Example 2 | 23 | 2 |
| Example 3 | 17 | 0 |
| Comparative example | 30 | 10 |
From the test results of foaming and defoaming, the sizing agent prepared by replacing part of rosin with the modified petroleum resin has less foaming and higher defoaming rate, and can effectively save the use of a defoaming agent.
It will be appreciated by persons skilled in the art that the above embodiments are by way of example only and are not limiting of the invention. The objects of the invention have been fully and effectively accomplished. The functional and structural principles of the present invention have been shown and described in the examples, and any variations or modifications of the embodiments of the present invention may be made without departing from the principles.
Claims (10)
1. A preparation method of a rosin substitute/cationic rosin sizing agent is characterized by comprising the following steps:
s1, polymerizing the petroleum cracking fraction at 50-70 ℃ under the action of an effective amount of cationic catalyst for 1-5h, adding maleic anhydride for graft modification at 210 ℃ at 170-6 h after the reaction is finished; cooling to 130 ℃ and 160 ℃, adding paraffin for 0.5-1h, and cooling to room temperature to obtain modified petroleum resin;
s2, mixing rosin and the modified petroleum resin according to the weight ratio of (70-95): (5-30), heating to 150 ℃, after the rosin and the modified petroleum resin are completely melted, adding a 90-95 ℃ cationic polymer emulsifier under high-speed stirring to obtain a metastable emulsion, homogenizing the metastable emulsion under high pressure, cooling and obtaining the rosin substitute/cationic rosin sizing agent.
2. The method of claim 1, wherein the petroleum cracking fraction is a C5 and/or C9 fraction.
3. The method according to claim 1, wherein the maleic anhydride is added in an amount of 5 to 20 parts by weight based on 100 parts by weight of the petroleum cracking fraction.
4. The method of claim 3, wherein the maleic anhydride is added in an amount of 5 to 10 parts.
5. The method of claim 1, wherein in step S1, the following amounts of each component are used by weight: 100 parts of petroleum cracking fraction, 5-10 parts of maleic anhydride and 4-10 parts of paraffin.
6. The method of claim 1, wherein the cationic catalyst in step S1 is selected from AlCl 3 、BF 3 、SnCl 4 、ZnCl 2 、TiCl 4 At least one of (1).
7. The method of claim 6, wherein the cationic catalyst is added in an amount of 0.4 to 1 wt% based on the petroleum cracking fraction.
8. The method of claim 1, wherein the cationic polymeric emulsifier in step S2 is a polyamide polyamine epichlorohydrin.
9. The method of claim 1, wherein the high pressure homogenization pressure in step S2 is 20-30 Mpa.
10. A rosin substitute/cationic rosin sizing agent prepared by the method of any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210756986.XA CN115058919A (en) | 2022-06-30 | 2022-06-30 | Preparation method of rosin substitute/cationic rosin sizing agent |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210756986.XA CN115058919A (en) | 2022-06-30 | 2022-06-30 | Preparation method of rosin substitute/cationic rosin sizing agent |
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| Publication Number | Publication Date |
|---|---|
| CN115058919A true CN115058919A (en) | 2022-09-16 |
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